Mechanical,thermal properties and isothermal crystallization kinetics of biodegradable poly(butylene succinate-<Emphasis Type="Italic">co</Emphasis>-terephthalate) (PBST) fibers

Biodegradable copolymer poly(butylene succinate-co-terephthalate) (PBST), with 70 mol% butylene terephthalate (BT), was melt-spun into fibers with take-up velocity of 2 km/min. The mechanical and thermal properties of the as-spun fibers were investigated through tensile test, DSC and TGA. Compared to poly(butylene terephthalate) (PBT) fibers, PBST fibers exhibited lower initial tensile modulus and higher tensile elongation at break which indicated their better flexibility. DSC results showed high melting temperature (ca.180.7 °C) of PBST fibers helpful to the textile processing compared to other biodegradable polyesters. Furthermore, isothermal crystallization behaviors of PBST fibers at low and high supercoolings were investigated by DSC and DLI, respectively. The measurement of crystallization kinetics at low supercoolings indicated that Avrami exponent n for PBST fibers was at a range of 2.9 to 3.3, corresponding to the heterogeneous nucleation and a 3-dimensional spherulitic growth. Similar results were given for isothermal crystallization behavior at high supercoolings investigated by DLI technique. Additionally, the equilibrium melting temperature of PBST fibers was obtained for 206.5 °C by Hoffman-Weeks method. Further investigation through DLI measurement provided the temperature at maximum crystallization rate for PBST fibers located at about 90 °C, which was very useful to polymer processing.     

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.     

The thermal,mechanical and viscoelastic properties of poly(butylene succinate-<Emphasis Type="Italic">co</Emphasis>-terephthalate) (PBST) copolyesters with high content of BT units

Poly(butylene succinate-co-terephthalate) (PBST) copolyesters, with rigid butylene terephthalate (BT) units varying from 50 to 70 mol%, were synthesized via direct esterification route. The chemical structure and comonomer composition were characterized by ¹H NMR. The weight-average molecular weights (M _w ) of the prepared products measured by GPC spanned a range of 1.39 × 10⁵–1.93 × 10⁵ with corresponding M _w /M _n value of 2.23–2.42. Based on the WAXD analysis, PBST copolyesters were identified to have the same crystal structure as that of poly(butylene terephthalate) (PBT). The researches on the thermal properties showed that the melting temperature and decomposed temperature of PBST copolyesters increased with the increasing content of rigid BT units through DSC and TGA measurement. Furthermore, the tensile test results presented that the copolyester with higher content of BT units had higher initial modulus, higher breaking strength but lower elongation at break. Additionally, the viscoelastic properties of the prepared PBST films were analyzed by DMA measurement. It was found that both storage modulus (E′) and loss modulus (E″) corresponding to the peak tended to heighten with the increase of BT units, indicating the copolyester with higher BT units content had the more prominent viscoelasticity. The peak of loss factor (tan δ) curve shifted to higher temperature as the content of rigid BT units increased due to the increasing of the glass transition temperature (T _g).     

Characterization on mixed-crystal structure of poly(butylene terephthalate/succinate/adipate) biodegradable copolymer fibers

Biodegradable poly(butylene terephthalate/succinate/adipate) (PBTSA) pellet, an ideal random copolymer characterized by ¹H solution NMR, was melt-spun into fibers. The crystal structure and physical properties of the as-spun fibers were investigated by WAXD, solid-state ¹³C NMR, DSC and tensile test measurements. Only poly(butylene terephthalate) (PBT)-like diffraction pattern was observed in WAXD; however, two different ¹³C spin-lattice relaxation time (T_1C) components were observed for aliphatic units, in which the longer and the shorter T_1C components correspond to the crystalline and the amorphous domains, respectively. Therefore the crystal structure of PBTSA was concluded to be formed by mixed crystallization of its comonomers. Such crystallization behavior enabled the PBTSA fibers to have well developed PBT-like crystal structure despite of its ideal randomness. Furthermore, due to the introduction of soft segments (BA and BS) into BT crystal lattice, melting temperature of PBTSA fibers (115 °C) was over 100 °C lower than that of PBT.     

Aliphatic–aromatic poly(butylene carbonate‐co‐terephthalate) random copolymers: Synthesis,cocrystallization, and composition‐dependent properties

A series of aliphatic–aromatic poly(carbonate‐co‐ester)s poly(butylene carbonate‐co‐terephthalate)s (PBCTs), with weight‐average molecular weight of 113,000 to 146,000 g/mol, were synthesized from dimethyl carbonate, dimethyl terephthalate, and 1,4‐butanediol via a two‐step polycondensation process using tetrabutyl titanate as the catalyst. The PBCTs, being statistically random copolymers, show a single T_g over the entire composition range. The thermal stability of PBCTs strongly depends on the molar composition. Melting temperatures vary from 113 to 213°C for copolymers with butylene terephthalate (BT) unit content higher than 40 mol %. The copolymers have a eutectic melting point when about 10 mol % BT units are included. Crystal lattice structure shifts from the poly(butylene carbonate) to the poly(butylene terephthalate) type crystal phase with increasing BT unit content. DSC and WAXD results indicate that the PBCT copolymers show isodimorphic cocrystallization. The tensile modulus and strength decrease first and then increase according to copolymer composition. The enzymatic degradation of the PBCT copolymers was also studied. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41952.     

紫外线吸收剂对PBST薄膜耐候性的影响

研究了聚（丁二酸丁二醇?对苯二甲酸丁二醇）酯（PBST）薄膜在吐鲁番、海南2地的自然老化行为，采用高速拉伸仪、加强型投射雾影仪、差示扫描量热仪（DSC）等对薄膜老化前后的拉伸性能、光学性能和热性能进行了测试和表征，探究紫外线吸收剂（UVA）对PBST薄膜耐候性的影响。结果表明，随自然老化时间的延长，PBST薄膜的拉伸强度、断裂伸长率逐渐下降，透光率无明显变化，雾度逐渐提高，熔融温度（T_m）向低温方向移动； UVA可显著改善PBST的耐候性，最适宜添加量为0.5 %（质量分数）。     

扩链改性聚对苯二甲酸丁二酯的力学性能研究

利用熔体流动速率测定仪、动态粘弹仪和电子拉力试验机等手段,考察了扩链改性对聚对苯二甲 酸丁二酯(PBT)的拉伸性能、熔体流动指数和动态力学性能的影响。实验结果表明:PBT经扩链改性后,随 其特性粘数增加,相对分子质量提高,熔体流动指数大幅度下降,玻璃化转变温度有所增加;改性后PBT的 储能模量和耗能模量提高2.6-4.6倍,拉伸强度提高50％以上,断裂伸长率提高1倍以上,表明扩链改性起 到了增粘增韧作用。     

Structure development and properties of high-speed melt spun poly(butylene terephthalate)/poly(butylene adipate-co-terephthalate) bicomponent fibers

Ultra-high-speed bicomponent spinning of poly(butylene terephthalate) (PBT) as sheath and biodegradable poly(butylene adipate-co-terephthalate) (PBAT) as core was accomplished with the take-up velocity up to 10 km/min. The structure development of the individual component and the properties of PBT/PBAT fibers were investigated through the measurements on differential scanning calorimetry, wide-angle X-ray diffraction, birefringence and tensile test. Due to the mutual interaction between two polymer-melts along the spinline, the processability of both components in PBT/PBAT bicomponent spinning was improved compared with those of corresponding single component spinnings. Furthermore, in PBT/PBAT fibers, the structure development of PBT component was found to be greatly enhanced, which led to the improvement in its thermal and mechanical properties; whereas the structure development of PBAT component was significantly suppressed, in which nearly non-oriented structure was observed in both crystalline and amorphous phases.     

静电纺丝PBT/PVA复合膜的制备及性能研究

以三氟乙酸和二氯甲烷为混合溶剂,采用静电纺丝法制备聚对苯二甲酸丁二酯(PBT)/聚乙烯醇(PVA)复合膜。用旋转粘度计和电导率仪测定溶液的黏度和电导率,用扫描电子显微镜、拉伸和水接触角测试PBT/PVA不同比例对纤维膜的形貌、力学和亲水性能的影响。结果表明,随着PVA比例的增加,混合溶液的黏度逐渐增大,而电导率先增大后减小;当PBT/PVA的比例为90/10时,纳米纤维的平均直径最小,为323 nm,而其纳米纤维膜的力学性能与纯PBT纤维膜相比显著提高,拉伸强度、弹性模量和断裂伸长率分别增加了213%,260%和57%;PVA的加入改善PBT纤维的亲水性,制备出力学性能优异且亲水的PBT/PVA纤维膜。     

Improvement of Mechanical Properties of Poly(butylene terephthalate)/Polyarylate Blends with Various Compositions via Zone Drawing-Zone Annealing

Abstract

Poly(butylene terephthalate)/polyarylate (PBT/PAr) blends of various compositions were subjected to a series of thermal and mechanical treatments. The evolution of the structure together with the static mechanical properties of produced fibers were investigated. It was found that zone drawing-zone annealing at 140 and 190[ddot] C markedly improves the blend mechanical properties: the Young modulus increases up to 5 times, the tensile strength-up to 10 times (compared to neat PBT) and up to 5 times (compared to neat PAr), the elongation at break drops 50–100 times with the rise of PAr content. The highest values of modulus and strength are obtained for blends containing between 10 and 35% (by wt) PAr. The observed improvement is explained by the substantial chain axis orientation and enhanced crystallization. of PBT offered by the zone drawing-zone annealing process, as proven by wide angle X-ray diffraction and birefrigent tests. Finally, a conclusion is drawn that after the appropriate treatments the PBT/PAr blends represent microfibrillar reinforced composites, similarly to other polymer blends for which the same improvements in the mechanical properties are known to be due to the microfibrillar reinforcing effect. The PBT microfibrils are visualized by observations using scanning electron microscope.     

Morphology and mechanical properties of injection molded articles with weld-lines

The effect of weld-lines on the morphology and mechanical properties of injection molded articles made of neat poly(butylene terephthalate) (PBT) and glass fiber-reinforced PBT was investigated. The weld-line was introduced to a molded article by using a rectangularly shaped insert inside a mold cavity, and tensile specimens were prepared at various positions through the entire molded article. The weld-line position was further checked by a short-shot experiment. Although the maximum tensile stress for specimens of neat PBT with a weld-line is almost the same as that without a weld-line, the maximum tensile stress and the elongation at break for fiber-reinforced PBT with a weld-line were found to be about half of those without the weld-line. This is attributed to the fact that the fibers near the weld-lines are oriented parallel to the weld-line direction (or perpendicular to the tensile force direction) due to stretching flow. Finally, we compared experimental results of flow pattern and fiber orientations with numerical simulations. We found that the predictions of flow fronts and fiber orientations are in good agreement with experimental results.     

Structure and properties of high-speed melt-spun filaments of poly(butylene terephthalate)

Filaments of poly(butylene terephthalate) were prepared by melt spinning with take-up velocities in the range 1000–5600 m/min. Two polymers with different molecular weights were used (intrinsic viscosities of 0.75 and 1.0 dL/g). The filaments were characterized using measurements of density, birefringence, shrinkage, thermal properties (differential scanning calorimetry), crystal size, crystalline orientation and phases present (wide angle X-ray diffraction), and tensile mechanical properties. Filaments spun from the 0.75 IV polymer with a mass throughput of 6 g/min at 1000 m/min have essentially amorphous structures, while higher take-up velocities result in α-form crystals or, at the highest take-up velocity, a mixture of α-form and β-form crystals. Only α-form crystals were detected in the higher IV polymer. Crystal size varied with crystallographic direction but generally increased as take-up velocity increased. At the lowest take-up velocities the filaments increased in length during thermal shrinkage measurements. With increasing take-up velocity the shrinkage became positive and continued to increase until reaching a maximum in the range of the highest sprinning speeds. This behavior correlates with the variation of the orientation factors of the amorphous phase. A plateau was observed in stress versus strain curves corresponding to strain-induced transformation from α-form to β-form crystals. The length of this plateau increased with increase of take-up velocity and the α-form crystal content in the sample. Both morphology and physical properties varied with polymer molecular weight and melt spinning conditions.     

纳米二氧化硅对PBT力学和结晶性能的影响

采用熔融共混的方法,将纳米SiO2添加到聚对苯二甲酸丁二醇酯(PBT)中,制备出PBT/纳米SiO2复合材料,对其力学和结晶性能进行分析研究。结果表明,随着纳米SiO2含量增加,PBT/纳米SiO2复合材料的拉伸强度和弯曲强度增加,PBT的结晶度增加,球晶尺寸减小,最大扭矩和平衡扭矩变化不大。当纳米SiO2含量为0.1份时,PBT的拉伸强度提高12%,断裂伸长率提高100%,冲击强度提高10%,弯曲强度提高5%,综合力学性能最好。     

Fibers from poly(ethylene terephthalate) and poly(butylene terephthalate) blends I. Mechanical behavior

Fibers prepared from poly(ethylene terephthalate) (PET) and poly(butylene terephthalate) (PBT) blends show a sharp decrease in tensile strength and modulus when blends are on the verge of phase segregation. The modulus values differ for homopolymers for their differences in chain configuration and methylene groups and that of the blends are in proportion. The experimental strength values are higher than the predicted values according to Paul's model for incompatible polymers. At 90/10 PET/PBT blend, the modulus is high, which may be a relative factor to the smaller crystal size of the components.     

生物基共聚酯PBSeT制备与性能

采用单釜酯化缩聚法合成了聚癸二酸-对苯二甲酸丁二酯(PBSeT),研究了对苯二甲酸和癸二酸配比对共聚酯PBSeT热性能和拉伸性能的影响.结果表明,共聚酯PBSeT的热性能和性能性能可以通过控制共聚单体的物质的量之比来调整.采用傅立叶变换红外光谱(FTIR)和核磁共振氢谱(1H NMR)表征了PBSeT的化学结构和组成,...     

Poly(butylene terephthalate)/organoclay nanocomposites prepared by in situ interlayer polymerization and its fiber (II)

Intercalated nanocomposites with poly(butylene terephthalate) (PBT) incorporated between the montmorillonite layers were synthesized from dimethyl terephthalate and 1,4-butane diol by using an in situ interlayer polymerization. The PBT nanocomposites were melt-spun at different organoclay contents to produce monofilaments. The samples were characterized by using wide angle X-ray diffraction, electron microscopy, thermal analysis, and tensile testing. The extent of the clay layer in the PBT was confirmed by using X-ray diffraction and electron microscopy, and the clay layer was found to be highly dispersed on a nanometer scale. The addition of only a small amount of organoclay was enough to improve the thermo-mechanical properties of the PBT hybrid fibers. The hybrids were extruded with various draw ratios (DRs) to examine the tensile mechanical property of the fibers. At DR=1, the ultimate tensile strength of the hybrid fibers increased with the addition of clay up to a critical content and then decreased. However, the initial modulus monotonically increased with increasing amount of organoclay in the PBT matrix. When the DR was increased from 1 to 6, for example, the strength and the initial modulus values of the hybrids containing 3 wt% organoclay decreased linearly.     

Structure and property studies of poly(trimethylene terephthalate) high-speed melt spun fibers

Poly(trimethylene terephthalate) has been melt spun at various take-up velocities from 0.5 to 8 km/min to prepare fiber samples. The effect of take-up velocity on the structure and properties of as-spun fibers has been characterized through measurements of birefringence, density, wide-angle X-ray scattering, DSC melting behavior, tensile properties and boiling water shrinkage (BWS). The birefringence exhibits a maximum at take-up velocities between 3 and 4 km/min. The fiber samples spun at the lower take-up speeds have essentially amorphous structures, while the filaments prepared at a velocity range higher than 4 km/min all possess an obvious crystalline structure. With increasing take-up speed, a steady improvement in tensile strength, elongation to break, and BWS is found, whereas the initial modulus remains almost constant within the measurement error, over the entire take-up speed range between 0.5 and 8 km/min.     

Structure formation in stretched sheets of poly(butylene terephthalate)

Crystalline and amorphous sheets of poly(butylene terephthalate) (PBT) were drawn in the temperature range of 20–150°C. The molecular orientation and the relative amount of α- and β-form crystals in the stretched sheets were studied by wide-angle X-ray diffraction (WAXD) and density measurements. When crystalline PBT sheets are drawn at lower temperatures, α-form crystals are partially transformed into β-form crystals. Both α- and β-form crystals are formed by drawing amorphous PBT sheets. The relative amount of α- and β-form crystals is much more sensitive to drawing temperature than to draw ratio. The α-form crystallinity is higher at higher drawing temperature and increases slightly with increasing draw ratio. The second moments of orientation functions of α- and β-form crystals increase with increasing draw ratio, and the increase of the orientation function is suppressed at higher draw ratio. The orientation function of α-form crystals is higher than that of β-form crystals in a same sample.     

Elastic response of copolyether-ester fiber on its phase morphology under different heat-treatment condition

In order to verify the elastic response of copolyether-ester (PEE) fibers on their phase morphology and structure, the PEE fibers based on poly(butylene terephthalate) (PBT) as hard segments and poly(terramethylene glycol) (PTMG) as soft segments were prepared by melt spinning, the as-spun fibers were then heat-drawn and heat-set at different conditions. From the analysis of the mechanical properties, it is shown that the tenacity as well as elastic recovery of the fibers increased with the increasing heat-draw ratios, the elongation at break decreased. The morphological and structural were evaluated by small angle X-ray scattering (SAXS), wide angle X-ray scattering (WAXS) and birefringence. When the melt-spun PEE fibers were heat-drawn, higher crystallinity and orientation, larger size of lamellae structure was formed within the fibers, it is also much easier to form higher phase separation. This structure will contribute to better elastic performances of PEE fibers.     

Fiber and film developments from immiscible blends of cellulose acetate propionate and poly(butylene terephthalate)

Binary blends of cellulose acetate propionate (CAP) and poly(butylene terephthalate) (PBT) in the composition range of 5–15 wt % for CAP were prepared in the form of films and fibers by compression molding and spinning, respectively. The presence of two invariant glass‐transition temperatures corresponding to the CAP and PBT components and viscosities lower than those of the neat PBT of the CAP–PBT blends implied that the CAP–PBT blends were immiscible. Moreover, the crystallinity of the PBT component was higher in the spun fibers than in the films; this was possibly due to the different cooling methods or the chain orientation in the spinning process. In the meantime, the CAP component could not undergo crystallization because of its rigid structure and alkyl substituents. For the CAP–PBT films, the amorphous CAP was present as dispersed particles in the PBT matrix; but it became rods in the spun fibers. In addition, the presence of the amorphous CAP resulted in a decrease in the tensile strength and an increase in the elongation at break for the CAP–PBT fibers. The CAP–PBT films and fibers could be applied in a wide range of applications requiring renewable properties. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45013.