Synthesis and Properties of Poly[p-(2,5-dihydroxy)-phenylenebenzobisoxazole] Fiber

The novel polymer poly[p-(2,5-dihydroxy)-phenylenebenzobisoxazole] (PBOH) fiber was synthesized in the presence of 2,5-dihydroxyterephthalicacid (DHTA) and 4,6-diamino-1,3-benzenediol in poly(phosphoric acid) (PPA) using typical polycondensation conditions. The crystalline solutions of liquid PBOH in PPA were spun into fibers using dry-jet wet spinning. Furthermore, the thermostability and mechanical properties of PBOH were compared with poly(p-phenylene-2,6-benzoxazole) (PBO) in order to investigate the relationship between the chain structure and properties. The results indicated that the thermal degradation temperature of PBOH was above 750K and the tensile strength of the PBOH fiber was 3.1GPa, which were much lower than those of PBO fiber. The compressive strength of PBOH fiber was 331 M Pa, which was slightly higher than that of PBO fiber. In addition, molecular simulation was employed to explain why the compressive strength of PBOH fiber did not increase significantly compared to PBO fiber.     

In Vitro Degradation Behavior of Polyesteramide Copolymer Fiber Based on 6-Aminocaproic Acid, Adipic Acid, and 1,6-Hexane Diol

In this work, a kind of aliphatic biodegradable polyesteramide (PEA) copolymer based on 6-aminocaproic acid, adipic acid, and 1,6-hexane diol was synthesized by melt polycondensation method, and was characterized by ¹H-NMR, FTIR and DSC. The PEA fiber was prepared by melt-spinning method. Tensile properties of the as-spun and hot-drawn fibers were also investigated. Hydrolytic degradation behavior of PEA copolymer chips and fibers were evaluated by weight loss in PBS solution with different pH value. The alkaline degradation behavior of fiber was also studied on change of diameter and surface morphology. During alkaline degradation, the PEA fiber underwent surface erosion. This work was financially supported by Chinese Key Basic Research Program (2004CB518800 and 2004CB518807), and Sichuan Key Project of Science and Technology (06(05SG022-021-02)).     

聚(对苯二甲酸-1,3-丁二醇酯/对苯二甲酸-1,4-丁二醇酯)/PEG嵌段共聚物的合成及性能研究

用熔融缩聚法合成了一系列聚(对苯二甲酸-1,3-丁二醇酯/对苯二甲酸-1,4-丁二醇酯)/聚乙二醇的嵌段共聚物。用FT-IR,1H-NMR,DSC,TGA,水降解测试等方法表征了材料的结构与性能。FT-IR和1H-NMR分析表明合成得到的共聚物为预期产物;DSC分析显示,共聚聚酯随着1,3-丁二醇在共聚物中比例的增大,熔点(Tm)逐渐降低,由158.24℃下降至104.19℃,玻璃化温度(Tg)逐渐升高,由4.86℃升至24.56℃,合成得到的共聚酯趋向于无定形态;TGA分析表明1,3-丁二醇在共聚酯中比例增大会使聚酯的热稳定性下降,但合成得到的共聚酯依然具有较好的热稳定性,初始分解温度大于310℃,不需要在反应过程中添加热稳定剂;水降解测试结果表明共聚物随1,3-丁二醇比例的增加,降解速率大幅提升。     

Synthesis,characterization, and hydrolytic degradation of biodegradable poly(ether ester)‐urethane copolymers based on ε‐caprolactone and poly(ethylene glycol)

In this article, a new kind of biodegradable poly(ε‐caprolactone)‐poly(ethylene glycol)‐poly(ε‐caprolactone)‐based polyurethane (PCEC‐U) copolymers were successfully synthesized by melt‐polycondensation method from ε‐caprolactone (ε‐CL), poly(ethylene glycol) (PEG), 1,4‐butanediol (BD), and isophorone diisocyanate (IPDI). The obtained copolymers were characterized by ¹H‐nuclear magnetic resonance (¹H‐NMR), FTIR, and gel permeation chromatography (GPC). Thermal properties of PCEC‐U copolymers were studied by DSC and TGA/DTG under nitrogen atmosphere. Water absorption and hydrolytic degradation behavior of these copolymers were also investigated. Hydrolytic degradation behavior was studied by weight loss method. ¹H‐NMR and GPC were also used to characterize the hydrolytic degradation behavior of PCEC‐U copolymers. The molecular weight of PCL block and PEG block in soft segment and the content of hard segment strongly affected the water absorption and hydrolytic degradation behavior of PCEC‐U copolymers. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Copolyesters developed from bio-based 2,5-furandicarboxylic acid: Synthesis,sequence distribution,mechanical, and barrier properties of poly(propylene-co-1,4-cyclohexanedimethylene 2,5-furandicarboxylate)s

A series of poly(propylene-co-1,4-cyclohexanedimethylene 2,5-furandicarboxylate)s (PPCFs) with different compositions were synthesized from bio-based aromatic monomer 2,5-furandicarboxylic acid and 1,3-propanediol (PDO), along with 1,4-cyclohexanedimethylene (CHDM). The chemical structure, composition, and sequence distribution of PPCFs were determined by nuclear magnetic resonance (¹H NMR and ¹³C NMR). Results showed that the compositions of copolyesters depended on the feed molar ratio of PDO and CHDM, and all the obtained PPCFs copolyesters had triad component in a random sequential structure. With the addition of CHDM, the gas barrier properties of poly(propylene 2,5-furandicarboxylate) (PPF) deteriorated. However, when the content of CHDM reached 79%, PPCF79 still showed the CO₂ and O₂ barrier improvement factor of 4.5 and 3.25, respectively, which were better than those of poly(ethylene naphthalate), a well-known polymer with barrier property. Besides, PPCF79 showed good performance on tensile modulus, tensile strength, elongation at break, and the crystallization enthalpy was improved from 3.2 J g⁻¹ for PPF to 30.7 J g⁻¹ for PPCF79. It has the potential to serve as a promising bio-based polymer with excellent comprehensive performance. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47291.     

PMDA-ODA型聚酰亚胺纤维的热稳定性研究

通过干法纺丝制备了聚酰亚胺(PI)纤维,采用热失重(TGA)测试分析了其热稳定性能.TGA测试表明,均苯四甲酸酐-4,4.二氨基二苯醚(PMDA-ODA)型PI纤维500℃之前不发生分解,其热分解稳定性要优于P84纤维.并利用Kissinger和Flynn-Wall-Ozawa方法计算并比较了PI和P84纤维在空气中热...     

Synthesis, characterization and biodegradation studies of poly(ester urethane)s

Bis-isocyanoto polyester was synthesized by the polymerization of PPSe with MDI and reacted with 1,3-propanediol chain extender to obtain poly(ester urethane)s. The effect of chain extender and PPSe content in polyurethane was investigated. The polymers were characterized by ¹H NMR, FT-IR, viscosity measurement, TGA and XRD. Their biodegradability was investigated by the hydrolytic degradation in NaOH solution (3% and 10%); enzymatic degradation by Rhizopus delemar lipase and soil burial degradation using garden-composted soil. Furthermore, the degraded film was characterized by molecular weight, intrinsic viscosity, DSC, XRD, FT-IR and surface morphology by SEM. The biodegradation study revealed that hydrolysis and soil burial degradation affected morphology of the PEUs. Hydrophobicity and hard segment seem to resist the hydrolytic and enzymatic degradability of PEU. Hydrolytic degradation was very rapid in 3% and 10% NaOH solutions at 37 °C, within 2 days 20% weight loss was observed. PEUs showed a much slower degradation rate under the R. delemar lipase at 37 °C. Experimental data showed that as soft segment increases biodegradation rate decreased. A significant rate of degradation was occurred in all PEU samples under soil burial condition. Surface morphology, which interconnected to good adhesion of bacteria on polymer surface, is considered to be a factor sensible for the biodegradation rate under soil burial condition.     

Nanomechanical properties of poly(trimethylene malonate) and poly(trimethylene itaconate) during hydrolytic degradation

The aim of this work was to evaluate surface mechanical properties of two bioplastics, poly(trimethylene malonate) (PTM) and poly(trimethylene itaconate) (PTI), during hydrolytic degradation. Renewable resource‐based PTM and PTI were synthesized from 1,3‐propanediol (PDO), malonic acid (MA), and itaconic acid (IA) via melt polycondensation. The hydrolytic degradation was performed in deionized (DI) water (pH 5.4) at room temperature. Morphology and surface mechanical properties at the nanoscale were monitored by atomic force microscopy (AFM) using a quantitative nanomechanical property mapping mode as a function of degradation time. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) were used to show shifted phase transitions depending on the degradation. DSC studies showed hydrolytic degradation induced crystallinity for PTI. After degradation for one week, the degree of crystallinity had significantly increased, and the elastic modulus of PTI had decreased by 58%. PTM was found to be hygroscopic. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41069.     

聚羟基丁酸-羟基戊酸共混干纺初生纤维的研究

将不同羟基戊酸(HV)含量的聚羟基丁酸-羟基戊酸共聚酯(PHBV)进行溶液共混,采用干法纺丝工艺获得PHBV共混纤维。通过SEM、DSC、XRD等仪器对所得纤维表面形态、热性能及力学性能随时间变化等进行了研究。结果表明,所得PHBV共混纤维表面有凹槽;随着共混HV含量的增高,PHBV共混纤维的熔点逐渐降低,结晶度逐渐减小;对于未经后处理的初生纤维,纺后4h内纤维的断裂伸长可达300%以上,断裂强度及断裂伸长也随着共混物中HV含量的增大而有所提高。通过共混降低了纤维脆性转变速率,为后续加工提供了性能良好的初生纤维。     

载体法制备聚四氟乙烯纤维及烧结工艺研究

以载体法制备出聚四氟乙烯纤维(PTFE)/聚乙烯醇(PVA)初生丝,然后对初生丝进行不同时间的烧结,以除去PVA制得PTFE纤维,对PTFE纤维进行不同程度的拉伸,检测不同烧结时间和拉伸倍数对纤维力学性能的影响。     

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.     

高速纺阳离子可染涤纶的结构与性能

用 DSC、TGA 方法分析比较了阳离子可染涤纶(ECDP)切片的结晶性能以及热稳定性能.用密度梯度法、声速法、S—S曲线、DSC、DDV 等方法对高速卷绕条件下的 ECDP 纤维进行了研究,得出了纺速对 ECDP 卷绕丝的影响规律,并对卷绕丝和 DT 丝的结构性质作了比较.本文还将 ECDP 与 PET 高速纺作了比较,从理论上解释了两者的差异.     

A novel TLCP blended with PET and PC matrices

This investigation focused on the potential of improving the performance of poly(ethylene terephthalate) (PET) and polycarbonate (PC) fibers by incorporating a novel thermotropic liquid crystalline copolymer (TLCP). The degree of mechanical enhancement obtained in the fibers incorporating 20 wt % TLCP depended upon the chosen matrix material and the processing conditions. The PET matrix systems did not exhibit any modulus improvements until after posttreatment of the fibers. Following posttreatment, the blends exhibited a modulus of 24 GPa, an increase of 40% compared to the PET control fiber. The PC systems exhibited a 1 GPa modulus increase in the as-spun fiber blends, but improvement was negligible after fiber posttreatment. The morphologies of the as-spun and posttreated fibers suggest that different mechanisms of reinforcement are occurring depending upon the matrix material selected. © 1994 John Wiley & Sons, Inc.     

Preparation of high performance PET fiber by solution spinning technique

High molecular weight poly(ethylene terephthalate) (PET, IV = 3.30 dL/g) was extruded in attempts to prepare high performance fiber using the solution spinning method. Solution preparation, fiber coagulation, and mechanical properties of resultant fibers were examined. An as-spun fiber exhibited high deformability when appropriate coagulation conditions were used. Tenacity and modulus of the resultant drawn fibers achieved 12.9 and 230 gpd, respectively, at draw ratio above 10. © 1995 John Wiley & Sons, Inc.     

Synthesis and characterization of novel biodegradable and biocompatible poly(ester-urethane) thin films prepared by homogeneous solution polymerization

Novel biodegradable and biocompatible poly(ester-urethane)s were synthesized by in situ homogeneous solution polymerization of poly(?-caprolactone) diol, dimethylolpropionic acid (DMPA), and methylene diphenyl diisocyanate in acetone followed by solvent exchange with water. The effects of the DMPA content and hard segment content on the properties of the polyurethanes were measured by DSC, TGA, and hydrolytic degradation measurements. The results showed that DMPA had a dramatic effect on the particle size; the particle size decreased rapidly with increasing DMPA content. The hydrolytic degradation test showed that the degradation rate was little affected by the DMPA content in the range investigated, but was observed to be influenced by the hard segment content. Cell toxicity analysis showed that the biodegradable poly(ester-urethane)s synthesized in this study did not exhibit any detectable toxicity to human umbilical vein endothelial cells and mouse embryonic stem cells. Both types of cells can effectively adhere to and spread on the surface of pure poly(?-caprolactone) or poly(ester-urethane)s. The present study demonstrates the feasibility of a facile synthesis of biodegradable polyurethanes and of their aqueous dispersions with prescribed properties for biomedical applications.     

Hydrolytic degradation and crystallization behavior of linear 2‐armed and star‐shaped 4‐armed poly(l‐lactide)s: Effects of branching architecture and crystallinity

“Linear” aliphatic polyesters composed of two poly(l ‐lactide) arms attached to 1,3‐propanediol and “star‐shaped” ones composed of four poly(l ‐lactide) arms attached to pentaerythritol (2‐L and 4‐L polymers, respectively) with number‐average molecular weight (M_n) = 1.4–8.4 × 10⁴g/mol were hydrolytically degraded at 37°C and pH = 7.4. The effects of the branching architecture and crystallinity on the hydrolytic degradation and crystalline morphology change were investigated. The degradation mechanism of initially amorphous and crystallized 2‐L polymers changed from bulk degradation to surface degradation with decreasing initial M_n; in contrast, initially crystallized higher molecular weight 4‐L polymer degraded via bulk degradation, while the degradation mechanism of other 4‐L polymers could not be determined. The hydrolytic‐degradation rates monitored by molecular‐weight decreases decreased significantly with increasing branch architecture and/or higher number of hydroxyl groups per unit mass. The hydrolytic degradation rate determined from the molecular weight decrease was higher for initially crystallized samples than for initially amorphous samples; however, that of 2‐L polymers monitored by weight loss was larger for initially amorphous samples than for initially crystallized samples. Initially amorphous 2‐L polymers with an M_n below 3.5 × 10⁴g/mol crystallized during hydrolytic degradation. In contrast, the branching architecture disturbed crystallization of initially amorphous 4‐L polymers during hydrolytic degradation. All initially crystallized 2‐L and 4‐L polymers had δ‐form crystallites before hydrolytic degradation, which did not change during hydrolytic degradation. During hydrolytic degradation, the glass transition temperatures of initially amorphous and crystallized 2‐L and 4‐L polymers and the cold crystallization temperatures of initially amorphous 2‐L and 4‐L polymers showed similar changes to those reported for 1‐armed poly(l ‐lactide). © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41983.     

Stereocomplex formation between enantiomeric poly(lactic acid). VIII. Complex fibers spun from mixed solution of poly(D-lactic acid) and poly(L-lactic acid)

To obtain poly(lactic acid) (PLA) complex fibers, spinning was performed by wet and dry methods from 5–10 g/dL chloroform solutions of poly(D-lactic acid) (PDLA) and poly(L-lactic), both with a viscosity-average molecular weight of 3 × 10⁵. The dope was extruded from a monohole nozzle into coagulation baths from ethanol and chloroform for wet spinning and into a drying column kept at 60°C for dry spinning. Scanning electron microscopic observation of the as-spun fibers showed that the surface of the wet-spun fiber had large basins with diameters of 50–100 μm and many pores with diameters from sub μm to 10 μm, whereas the surface of dry-spun fiber had a microporous structure with the pore diameter of 1–3 μm. The tensile strength of the wet-spun complex fiber was very low and could not be drawn at high temperatures, in contrast to the dry-spun fiber. The tensile strength of dry-spun complex fiber increased upon hot drawing and showed the tensile strength of 94 kg/mm² by drawing at 160°C to the draw ratio of 13. Differential scanning calorimetry revealed that the complex fibers contained both the stereocomplex crystallites (racemic crystallites) and the crystallites of the single polymers, PDLA and PLLA, regardless of the spinning methods. The ratio of the racemic crystallites to the single-polymer crystallites increased with the draw ratio of the complex fiber. © 1994 John Wiley & Sons, Inc.     

Effects of Basic Chemical Surface Treatment on PBO and PBO Fiber Reinforced Epoxy Composites

The effects of chemical surface treatment on PBO fiber and its composite materials were investigated using a basic sodium hydroxide solution. We evaluated several important treatment parameters quantitatively, including treatment concentration, treatment temperature and treatment time. Both as-spun (AS) and high-modulus (HM) PBO fibers were studied. The results showed that PBO fibers exhibited minimum or negligible reduction in their tensile strengths after the proposed treatment processes. The fibers’ contact angles with several liquid media were greatly reduced and the surface free energy could be increased to 58 mJ/m² or by 17%. The interfacial shear strength between PBO fiber and the epoxy matrix was improved to 38 MPa or by 11% with the same treatment process. The composite’s failure mode also shifted from fiber/matrix interface adhesive failure to partly cohesive failure.     

静电纺氧化铝纤维的制备工艺

分别以聚乙烯吡咯烷酮(PVP)和乙酰丙酮铝作为聚合物和氧化铝前驱体,利用溶胶-凝胶法和静电纺丝技术,在合适的工艺条件下得到了形态良好的氧化铝初生混合纤维,并于1300℃烧结1 h后,得到了直径在200 nm左右的α-氧化铝纤维。透射电子显微镜(TEM)结果表明:α-氧化铝纤维是由无数尺寸在7～12 nm之间的晶粒相互融合形成的。研究了不同的升温速率对于氧化铝纤维形态的影响,结果表明:升温速率越小,越有利于氧化铝纤维的成形。通过将初生纤维于不同温度下烧结,讨论了其在热处理过程中的晶相衍变历程。     

Spinning speed–throughput rate relationships for polyester,nylon, and polypropylene fibers

The relationship between spinning speed and throughput rate has been investigated for fibers having the same fiber denier in the drawn state when produced by melt spinning of poly(ethylene terephthalate), nylon 6, and polypropylene polymers over a range of take-up speed (750–3000 m min^-1) and throughput rate. To understand the structural origin of the relationship, a limited amount of characterization of structure and properties of the as-spun and drawn fibers was also done. A comparison of the results for the three polymers shows that while the increase in productivity with increase in spinning speed is relatively less for polyester and nylon 6, it is quite high for polypropylene. The birefringence data show that while molecular orientation increases rapidly with increasing wind-up speed in polyester and nylon 6, the rate of increase is relatively less in the case of polypropylene. The possible reasons for the observed differences in behavior are discussed. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:1773–1788, 1997