PBS/PBAT共混型全生物降解材料的制备及其性能研究

通过熔融共混法制备了聚丁二酸丁二醇酯（PBS）/聚己二酸对苯二甲酸丁二酯（PBAT）共混物,用熔体流动速率法、扫描量热法、X射线衍射、扫描电镜法及力学性能测试等手段研究了PBS/PBAT共混物的熔体流动性、结晶性能、力学性能以及共混物相容性。结果表明,随着PBAT含量的增加,PBS/PBAT共混体系的拉伸强度先升高后降低,断裂伸长率不断提高,冲击强度先降低后提高;当PBAT含量为20 %（质量分数,下同）时,与纯PBS相比,断裂伸长率提高10倍,冲击强度提高82 %,而拉伸强度仅仅降低6 %。     

Characterization on mixed-crystal structure and properties of poly(butylene adipate-co-terephthalate) biodegradable fibers

Biodegradable ideal random copolymer poly(butylene adipate-co-terephthalate) (PBAT), with 44 mol% butylene terephthalate (BT), was melt-spun into fibers with take-up velocity up to 5 km/min. The structure development and properties of the as-spun fibers were investigated through birefringence, WAXD, SAXS, DSC and tensile test. Despite of the ideal randomness and composition (1:1) of PBAT copolymer, PBAT fiber showed well-developed PBT-like crystal structure, while its melting temperature (ca. 121 °C) was over 100 °C lower than that of PBT. Based on the quantitative analyses on the lattice spacing, the crystallinity and the fraction of crystallizable BT sequences, the crystal structure of PBAT was characterized to be formed by mixed-crystallization of BT and BA units, where BA units were incorporated into BT lattice. This mixed-crystal structure was found to undergo PBT-like reversible crystal modification with the application and removal of tensile stress. This crystal modification was found to occur in a higher strain region compared with that of PBT fibers.     

Electrospinning and structural characterization of ultrafine poly(butylene succinate) fibers

Biodegradable ultrafine poly(butylene succinate) (PBS) fibers were continuously electrospun for the first time from PBS solutions in chloroform (CF)/2-chloroethanol (CE) (7/3, w/w), CF/CE (6/4, w/w), dichloromethane (DM)/CE (7/3, w/w), DM/CE (6/4, w/w), and CF/3-chloro-1-propanol (9/1, w/w). These mixed solvents had an appropriate evaporation rate for the continuous electrospinning of PBS. The ultrafine PBS fibers had very high crystallinity and their average diameters were in the range of 125-315 nm. The annealed ultrafine PBS fibers exhibited a lamellar stack morphology containing crystalline and amorphous layers.     

Morphological study on three kinds of two-dimensional spherulites of poly(butylene terephthalate) (PBT)

Three kinds of thin film specimens, each of which containing one of the three types of two-dimensional poly(butylene terephthalate) (PBT) spherulites (i: usual-positive type, ii: usual-negative type, and iii: unusual type), were prepared and studied mainly by transmission electron microscopy. It was confirmed that all these kinds of spherulites are made up of only the α-modification crystals, and the growth directions for usual-positive type, usual-negative type, and unusual type are the [010]^∗, ^∗, and ^∗ directions in the reciprocal lattice, respectively. Furthermore, the arrangement of unit cell in each type of the spherulites was determined. The relationships between the arrangements of unit cell and the types of each resulting spherulite are discussed.     

DSC and TMDSC study of melting behaviour of poly(butylene succinate) and poly(ethylene succinate)

The subsequent melting behaviour of poly(butylene succinate) (PBSU) and poly(ethylene succinate) (PES) was investigated using DSC and temperature modulated DSC (TMDSC) after they finished nonisothermal crystallization from the melt. PBSU exhibited two melting endotherms in the DSC traces upon heating to the melt, which was ascribed to the melting and recrystallization mechanism. However, one melting endotherm with one shoulder and one crystallization exotherm just prior to the melting endotherm were found for PES. The crystallization exotherm was ascribed to the recrystallization of the melt of the crystallites with low thermal stability, and the shoulder was considered to be the melting endotherm of the crystallites with high thermal stability. The final melting endotherm was ascribed to the melting of the crystallites formed through the reorganization of the crystallites with high thermal stability during the DSC heating process. TMDSC experiments gave the direct evidences to support the proposed models to explain the melting behaviour of PBSU and PES crystallized nonisothermally from the melt.     

Synthesis and thermal characterization of poly(butylene terephthalate-co-thiodiethylene terephthalate) copolyesters

Poly(butylene terephthalate-co-thiodiethylene terephthalate) copolymers of various compositions were synthesized and characterized in terms of chemical structure and molecular weight. The thermal behavior was examined by thermogravimetric analysis and differential scanning calorimetry. All the polymers under investigation show a good thermal stability. At room temperature they appear as semicrystalline materials: the main effect of copolymerization was a lowering in the amount of crystallinity and a decrease of melting temperature with respect to homopolymers. A pure crystalline phase has been evidenced at high content of butylene terephthalate or thiodiethylene terephthalate units and Baur's equation was found to describe well the T_m-composition data. Amorphous samples (containing 50-100 mol% of thiodiethylene terephthalate units) showed a monotonic decrease of T_g as the content of sulfur-containing units is increased, due to the presence of flexible C-S-C bonds in the polymeric chain. Finally, the Fox equation described well the T_g-composition data.     

Stretch-induced bidirectional polymorphic transformation of crystals in poly(butylene adipate)

Stretch-induced structural changes of poly(butylene adipate) at various temperatures were systematically investigated by X-ray diffraction method. It was found that tensile deformation could lead to both occurrence of α to β and β to α crystal transition via solid–solid process. Experimental results shows that either α or β form can be adopted as the stable phase for PBA crystal depending on the competition between tensile strain and temperature. Higher temperature favors β to α crystal transformation, while larger strain would result in α to β crystal transformation. Due to the conversion of crystal stability during stretching, a unique “β to α to β” transformation phenomenon of PBA appears at appropriate temperature for original β spline. This study provides evidence that both temperature and tensile strain can alter the relative stability of polymorphic crystals of semi-crystalline polymers.     

Epitaxial crystallization of poly(butylene adipate) on highly oriented isotactic polypropylene thin film

The crystallization behaviors of PBA on highly oriented iPP substrate both from solution and isotropic melt were studied by means of optical microscopy, AFM, X-ray and electron diffractions. The results clearly indicate the occurrence of heteroepitaxy of PBA on the iPP substrate in its β-form with both molecular chains ±50° apart from. This is based on the existence of perfect matching between the interchain distance of β-PBA along [100] direction and the distance of the out-sticking methyl side group arrays along the [101] direction of the (010) iPP plane. Electron diffraction pattern further confirms that the (010) lattice plane of the β-PBA is in contact with the iPP substrate.     

Dielectric spectroscopy of poly(butylene succinate) films

Dielectric properties of poly(butylene succinate) crystallized under different conditions have been reported in the temperature range of 163-383 K and in the frequency range of 0.01-10⁵ Hz. Both the dipolar α and β processes have been identified at low temperatures: the α process is associated with the amorphous fraction while the β with the relaxations in both the amorphous and crystalline fractions. The space charge effect dominates the high temperature dielectric spectra. These spectra have been analyzed in the light of an equivalent circuit model. The Maxwell-Wagner-Sillars polarization, electrode polarization and free charge motion are well resolved. At 383 K, near the melting temperature (387 K), massive melting and subsequent recrystallization have been observed. The peculiar evolution of the spectra is also analyzed using the same equivalent circuit model. The relationship between the fitting parameters and the evolved microstructures is discussed.     

Hydrolytic stability of sulfonated poly(butylene terephthalate)

The hydrolysis of sulfonated poly(butylene terephthalate) copolymers was studied. Sulfonated poly(butylene terephthalate) copolymers, referred to as PBT-ionomers (PBTIs), were shown to hydrolyze faster than poly(butylene terephthalate) (PBT). An experiment designed to isolate the effect of the sulfonated isophthalate (SIP) moieties on hydrolysis rate showed that the SIP moieties were responsible for the faster hydrolysis. Experiments aimed at identifying the mechanism of influence of the SIP moieties on hydrolytic stability indicated that hydrolysis was enhanced by the presence of ionic multiplets which increase amorphous content, imbibe water, and perhaps exert a medium effect on the hydrolysis of esters associated with the ionic groups.     

Toughening of poly(butylene terephthalate) by AES terpolymer

AES, a terpolymer of acrylonitrile-EPDM(ethylene/propylene/diene elastomer)-styrene, was blended in poly(butylene terephthalate) (PBT). Uniaxial tensile tests were carried out at various strain rates on blends containing 0-50 wt% of AES in order to study the yielding behavior of PBT in these blends by the Eyring equation. It was found that stress concentration factor (γ) increases sharply when a small content of AES is incorporated in the PBT matrix, but further incorporation seems to have small effect and γ levels out, a behavior that can be explained by the blend morphology and AES mechanical characteristics. The effect of AES content on the notched Izod impact strength of PBT blends was also examined in depth. It was found that a supertough blend can be achieved with at least 30 wt% of AES in PBT in appropriate molding temperature. Macroscopic and microscopic observations indicate that dilatational process play an important role on the toughening mechanism in PBT/AES blends at notched Izod impact tests.     

Crystallization behavior of poly(butylene succinate)/corn starch biodegradable composite

The effects of corn starch (CS) filler and lysine diisocyanate (LDI) as a coupling agent on the crystallization behavior of a poly(butylene succinate) (PBS)/CS ecocomposite were investigated using differential scanning calorimetry. In isothermal crystallization, n values for pure PBS were from 2.33 to 2.82. On the other hand, both composites showed values of 3 < n < 4. In nonisothermal crystallization, the Avrami exponent varied from 2.12 to 2.55 for pure PBS, from 1.58 to 1.96 for the composite without LDI, and from 1.79 to 1.91 for the composite with LDI, depending on the cooling rate. There was not a large difference of the crystallization rate constant (k) as adjusted by the Jeziornay suggestion. The activation energy for nonisothermal crystallization was also calculated on the basis of three different equations (Augis–Bennett, Kissinger, and Takhor equations). However, the values of the activation energy were in contradiction with the results of the kinetics. The addition of the filler (CS) and coupling agent (LDI) affected the morphological structure of PBS spherulites. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1107–1114, 2005     

Toughening of poly(butylene terephthalate) with epoxy-functionalized acrylonitrile-butadiene-styrene

Glycidyl methacrylate (GMA) functionalized acrylonitrile-butadiene-styrene (ABS) copolymers have been prepared via an emulsion polymerization process. These functionalized ABS copolymers (ABS-g-GMA) were blended with poly(butylene terephthalate) (PBT). DMA result showed PBT was partially miscible with ABS and ABS-g-GMA, and DSC test further identified the introduction of GMA improved miscibility between PBT and ABS. Scanning electron microscopy (SEM) displayed a very good dispersion of ABS-g-GMA particles in the PBT matrix compared with the PBT/ABS blend when the content of GMA in PBT/ABS-g-GMA blends was relatively low (<8 wt% in ABS-g-GMA). The improvement of the disperse phase morphology was due to interfacial reactions between PBT chains end and epoxy groups of GMA, resulting in the formation of PBT-co-ABS copolymer. However, a coarse, non-spherical phase morphology was obtained when the disperse phase contained a high GMA content (≥8 wt%) because of cross-linking reaction between the functional groups of PBT and GMA. Rheological measurements further identified the reactions between PBT and GMA. Mechanical tests showed the presence of only a small amount of GMA (1 wt%) within the disperse phase was sufficient to induce a pronounced improvement of the impact and tensile properties of PBT blends. SEM results showed shear yielding of PBT matrix and cavitation of rubber particles were the major toughening mechanisms.     

Synthesis of novel biodegradable poly(butylene succinate) copolyesters composing of isosorbide and poly(ethylene glycol)

A series of biodegradable isosorbide‐based copolyesters poly(butylene succinate‐co‐isosorbide succinate‐co‐polyethyleneoxide succinate) (PB_xI_yE_zS) were synthesized via bulk polycondensation in the presence of dimethyl succinate (DMS), 1,4‐butanediol (BDO), poly(ethylene glycol) (PEG) and isosorbide (ISO). The crystallization behaviors, crystal structure and spherulite morphology of the copolyesters were analyzed by differential scanning calorimetry (DSC), wide angle X‐ray diffraction (WAXD) and polarizing optical microscopy (POM), respectively. The results indicate that the crystallization behavior of the copolyesters was influenced by the content of isosorbide succinate (IS) and polyethyleneoxide succinate (PEOS) units, which further tuned the mechanical and biodegradable properties of the copolyesters. The PB_xI_yE_zS copolyesters, compared to pure poly(butylene succinate), showed lower crystallization temperature, melting temperature, degree of crystallinity and degradation rate while a significant increase in glass transition temperature with increasing isosorbide content. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Enzymatic degradation kinetics of poly(butylene succinate) nanocomposites

In this work, poly(butylene succinates) (PBS)/organically modified layered silicates (OMLS) composites were prepared by solution blending. The degradability of PBS, PBS/layered silicates and PBS/OMLS nanocomposites have been investigated using enzymatic degradation method. Effects of layered silicates and OMLS contents on the degradation behavior of PBS were explored. The results reveal that the degradability of the composites was both enhanced by the addition of layered silicates or OMLS as compared to the pristine PBS sample. The calculated data based on the autocatalytic model show that the degradation kinetics of PBS/layered silicates composites is the chain scission process with the following autocatalytic reactions, which is very similar to that of pure PBS matrix. On the other hand, the surface-catalyzed reaction model may be more suitable to describe the degradation behavior of the PBS/OMLS nanocomposite. Moreover, the results show that rate-controlling step of the degradation reaction for PBS/OMLS nanocomposite is more probable to be the desorption step.     

Effects of polymer concentration and zone drawing on the structure and properties of biodegradable poly(butylene succinate) film

To produce various biodegradable poly(butylene succinate) (PBS) films for particular use, the effects of initial polymer concentration and zone drawing on the structure, physical properties, and hydrolytic degradation of PBS film were investigated. PBS films were prepared from chloroform solutions with different initial concentrations of 8, 11, 14, 17 and 20 g/dl. In order to investigate the drawing behavior of the PBS films with different solution concentrations, the films were drawn under various zone drawing conditions. Through a series of experiments, it turned out that the initial concentration of PBS solution in chloroform caused significant changes in the draw ratio of the PBS film. That is, the zone draw ratios of the film at initial concentration of 14 g/dl exhibited its maximum values and gradually decreased at higher or lower concentrations. Thus, it was concluded that the initial concentration of 14 g/dl is the optimum polymer concentration to produce maximum draw ratio in this work. In addition, the crystal and amorphous orientations and tensile properties of PBS film having similar draw ratio and similar crystallinity were highest at 14 g/dl and surface crystal morphologies of these films were absolutely different. The hydrolytic degradation rate of the film at 14 g/dl was lowest, but with similar draw ratio, film dimension, and crystallinity, indicating that the degradation behaviors were greatly affected by the initial polymer concentration, orientation, and crystal morphology.     

Characterization of poly(trimethylene/butylene terephthalate) copolymer prepared by the copolycondensation of bis(3‐hydroxypropyl terephthalate) and bis(4‐hydroxybutyl terephthalate)

Homopolymers and copolymers were synthesized by polycondensation and copolycondensation, with varying feed ratios of bis(3‐hydroxypropyl terephthalate) (BHPT) and bis(4‐hydroxybutyl terephthalate) (BHBT) at 270°C. In addition, in the mol ratio of 1:1, copoly(trimethylene terephthalate/butylene terephthalate) [P(TT/BT)], with reaction times of 5, 10, 20, 30, and 60 min, was synthesized to identify the chain‐growth process of the copolymers. From differential scanning calorimetry (DSC) data, it was found that a random copolymer might be formed during copolycondensation. The molecular structure of copolymers, formed through the interchange reaction of BHPT and BHBT, was investigated using carbon nuclear magnetic resonance spectroscopy (¹³C‐NMR). We calculated the sequence‐length distributions of trimethylene and butylene sequences and randomness in the copolymers using ¹³C‐NMR data. From the values of the number‐average sequence length calculated, it was determined that a random copolymer was produced: This result coincides with previous DSC data. The lateral spacing of the unit cell of the copolymer increased slowly when the mol percent of one monomer was increased to that of the other monomer, indicating broadening of the unit cell by lateral distortion. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2200–2205, 2003     

Blends of poly(ethylene terephthalate) and poly(butylene terephthalate)

Commercial grade poly(ethylene terephthalate), (PET, intrinsic viscosity = 0.80 dL/g) and poly(butylene terephthalate), (PBT, intrinsic viscosity = 1.00 dL/g) were melt blended over the entire composition range using a counterrotating twin‐screw extruder. The mechanical, thermal, electrical, and rheological properties of the blends were studied. All of the blends showed higher impact properties than that of PET or PBT. The 50:50 blend composition exhibited the highest impact value. Other mechanical properties also showed similar trends for blends of this composition. The addition of PBT increased the processability of PET. Differential scanning calorimetry data showed the presence of both phases. For all blends, only a single glass‐transition temperature was observed. The melting characteristics of one phase were influenced by the presence of the other. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 75–82, 2005     

Synthesis and characterization of poly[(butylene succinate)‐co‐(butylene terephthalate)]‐b‐poly(tetramethylene glycol) segmented block copolymer

Polyester‐polyether segmented block copolymers of poly[(butylene succinate)‐co‐poly(butylene terephthalate)] (PBS–PBT) and poly(tetramethylene glycol) (PTMG) (M_n = 2000) with various compositions were synthesized. PBT content in the PBS was adjusted to ca. 5 mol %. Their thermal and mechanical properties were investigated. In the case of copolymer, the melting point of the PBS–PBT control was 107.8°C, and the melting point of the copolymer containing 70 wt % of PTMG was 70.1°C. Crystallinity of soft segment was 5 ∼ 17%, and that of hard segment was 42 ∼ 59%. The breaking stress of the PBS–PTMG control was 47 MPa but it decreased with increasing PTMG content. In the case of copolymer containing 70 wt % of PTMG, breaking stress was 36 MPa. Contrary to the decreasing breaking stress, breaking strain increased from 300% for PBS–PBT control to 900% for a copolymer containing 70 wt % of PTMG. The shape recovery ratios of the copolymer containing 70 wt % PTMG were almost twice of those of copolymers containing 40 wt % PTMG. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2067–2075, 2001