Polyester-Polyether Block Copolymers III. Supramolecular Texture in Poly(hexamethylene terephthalate)/Poly(oxytetramethylene) Block Copolymers and Related Homopolymers and Blends

Optical and electron microscopy and small-angle X-ray scattering have been used to investigate the texture of poly(hexamethylene terephthalate)/poly(oxtetramethylene) multi-block copolymers. The findings are consistent with a substantial separation of the combined sub-species into separate phases, and with the aggregation of the alkylene terephthalate ‘hard’ segment blocks into crystalline forms analogous to those of the homopolymer alone and connected by microfibrillar units. The observations are correlated with the mechanical properties of the copolymers in terms of a ‘string of beads’ model, and compared with existing knowledge of phase-separation morphology in other families of block copolymers. Some investigation has also been made into the morphology of poly(hexamethylene terephthalate) and poly(oxytetramethylene) homopolymers and their blends crystallised from the melt. The results are considered in relation to the properties of the corresponding copolymers.     

PTT/PETG共混物的热性能和结晶行为研究

主要研究了PTT/PETG共混物的热性能和结晶行为。DSC实验表明:PTT/PETG共混物只有一个Tg,说明两者在无定形区相容性好,而且随着PETG组分的增加,Tg增大。PTT/PETG两组分含量接近时,出现2个结晶峰。热失重分析结果表明:两组分相差较大时,随着PETG含量的增加,共混体系的热稳定性提高。通过观察共混物的结晶形态表明:PTT/PETG为80/20时,其球晶尺寸较大。     

Miscibility,Mechanical and Thermal Properties of Melt-Mixed Poly(trimethylene terephthalate)/Polypropylene Blends

This study examined the miscibility, mechanical and thermal properties of melt-mixed blends of PTT(poly(trimethylene terephthalate)) with PP(isotatic polypropylene). DMA and SEM results indicated that the PTT/PP blends are immiscible. Revealed from TGA analyses, the blends with a higher PP content showed a higher degradation temperature. A complex melting behavior was observed for the blends. The isothermal crystallization kinetics of the blends was analyzed from 200°C to 210°C using the Avrami equation. The WAXD results showed that the crystal structure of PTT remained unchanged in the blends. Nevertheless, the PP rich blends possessed lower tensile strength and higher elongation at break.     

Polyester-polyether block copolymers. I. Wide-angle X-ray diffraction studies of poly(hexamethylene terephthalate)/poly(oxytetramethylene) and related block polymers

The crystallisation and orientation of the individual structural components of poly(hexamethylene terephthalate)/poly(oxytetramethylene) block copolymers have been studied by wide-angle X-ray diffraction. The crystallisation behaviour in the unstretched state is determined by the proportions and molecular weights of the polyether blocks. For copolymers containing less than 60 wt% of polyether of m. w. ≯ 2000, only the polyester segments crystallise spontaneously, but with polyether m. w > 2000 two crystalline phases are formed. Similar behaviour was found in block polymers from other readily crystallising polyesters, but with non-crystallising polyesters the polyether segments crystallised spontaneously. Moderate tensile deformation of the block copolymers from polyether of m. w. 2000 leads to the stress-reversible highly oriented crystallisation of the polyether whilst the polyester remains undeformed. At higher extensions, irreversible orientation of the polyester segments occurs. The observations suggest that the polyester and polyether segments form discrete regions since otherwise homogeneous crystallisation should occur.     

Mechanical and Rheological Properties of Poly(ethylene terephthalate)/ Polypropylene Blends

Poly(ethylene terephthalate) and polypropylene (PET/PP) were compounded and pelletized with a single-screw extruder. Standard ASTM tensile test specimens were made by injection moulding. The blends are stronger and stiffer than the plain PP specimens. The addition of a compatibilizer, EPOLENE E-43, is found to improve the strength and stiffness of the blends at loadings of 50% and 70% PET. At 10% PET loading, E-43 has the opposite effect of slightly reducing the tensile properties. All the blends are more brittle relative to either plain PET or PP. The addition of E-43 results in negligible improvement in the elongation at break. E-43 is also found to be an effective lubricant in improving the processability of the blends. The blends with E-43 added have lower viscosities and less shear-thinning characteristics than those without E-43. © 1997 SCI.     

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。     

Mechanical and Thermal Properties of Poly(Phthalazinone Ether Sulfone)/Poly(Ether Sulfone) Blends

The mechanical and thermal properties of poly(phthalazinone ether sulfone) (PPES)/poly(aryl ether sulfone) (PES) blends prepared by melt-mixing were investigated by dynamic mechanical thermal analysis (DMTA) and thermogravimetric analysis (TGA). The dynamic mechanical thermal analysis results show that the incorporated PES has a large influence on the heat stability of PPES. The DMTA results display that the blends with a single glass transition temperature, which increases with increasing PPES content, indicates that PPES and PES are completely miscible over the studied composition range. The thermodegradative behavior of PPES/PES blends was used to analyze their thermal stability. The Friedman technique was used to determine the kinetic parameters (i.e., the apparent activation energy and order of reaction of the degradation process). The results indicate that the presence of the PES component influences the thermal stability of the PPES. On the basis of the kinetic data derived from Friedman' approach, the lifetime estimates for pure PPES, pure PES, and the blends generated from the weight loss of 5% were constructed.     

Thermal and Mechanical Properties of Polyblends of Polycaprolactam with Cationic Dyeable Poly(ethylene terephthalate)

One Polycaprolactam (PCPL) polymer and three cationic dyeable poly(ethylene terephthalate) (CD-PET) polymers were blended mechanically in the proportions of 90/10, 80/20, 70/30, 60/40, 50/50, 40/60, 30/70, 20/80, 10/90 in a melt twin-screw extruder to prepare twenty-seven PCPL/CD-PET polyblended polymers. The molar ratios of 5-sodium sulfonate dimethyl isophthalate (5-SSDMI) for three CD-PET polymers were 2, 6 and 10%, respectively. This study investigated the thermal and mechanical properties of PCPL/CD-PET polyblended materials using gel permeation chromatograph (GPC), nuclear magnetic resonance (NMR), gas chromatography (GC), potentiometer, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), scanning electron microscope (SEM), extension stress-strain measurement, density gradient method and rheometer. Experimental results of the thermal properties indicated PCPL and CD-PET molecules easily formed individual domains. PCPL and CD-PET polymers were proved to be immiscible system even when CD-PET possessed higher 5-SSDMI content. Rheological behaviour of PCPL/CD-PET polyblends exhibited negative-deviation blends (NDB). The measurements of densities showed linear variation with the blend ratio of PCPL/CD-PET polyblends. The SEM pictures displayed the blend ratio of PCPL/CD-PET was 50/50, the morphological aggregation of a larger size from 3 to 5 m in diameter was observed. Experimental results of the mechanical properties indicated the 50/50 blend of PCPL/CD-PET showed a minimum tensile strength.     

Morphology,Thermal and Mechanical Properties of Biodegradable Poly(butylene succinate)/Poly(butylene adipate-co-terephthalate)/Clay Nanocomposites

Sodium montmorillonite (Na-MMT) was successfully modified by octadecylamine (ODA) through a cation exchange technique that showed by the increased of basal spacing of clay by XRD. The addition of the organoclay into the PBS/PBAT blends produced intercalated-type nanocomposites with improvements in tensile modulus and strength. The highest tensile strength of nanocomposite was observed at 1 wt% of organoclay incorporated. A TGA study showed that the thermal stability of the blend increased after the addition of the organoclay by 1 wt%. SEM micrographs of the fracture surfaces show that the morphology of the blend becomes smoother with presence of organoclay.     

PET/PTT共混聚酯的等温结晶行为

使用差示扫描量热仪(DSC)研究不同比例的PET/P1T共混聚酯在205℃的等温结晶行为,并使用Avrami方程对其等温结晶过程进行研究.结晶半周期t1/2,总结晶速率常数k和Avrami指数n的变化表明:在共混体系中,对于PET和PTT而言,另一组分的加入都会对结晶产生阻碍作用,PET与P1T相互影响成核与晶体生长机理.     

Properties of Block Copolymers of Poly(Butylene Terephthalate) and Polyoxytetramethylene Glycol

Synthesis of polyester thermoelastoplasts, block copolymers of polyoxytetramethylene glycol and poly(butylene terephthalate) of the polyblock type, was developed and implemented in pilot industrial conditions. POTM blocks act as flexible molecular decouplings that give the copolymer elasticity, while PBT blocks form physical linkages and are responsible for the mechanical strength and hardness of the material. The composition of the reaction systems, process stage sequence, and synthesis parameters are optimized for block copolymers with a concentration of the flexible POTM block of 65-10 wt. % and a molecular weight of 1000. The structure is investigated, and the physicochemical and mechanical properties of the material obtained are determined. It was found that the concentration of flexible blocks has a determining effect on the physicochemical structure and properties of the block copolymers. For a 40% concentration of the flexible block, the character of the concentration curves of the physicomechanical indexes changes significantly due to phase-structural transformations in the block copolymers.     

Structural investigation of Poly(ethylene terephthalate)/Poly(trimethylene terephthalate) transesterificated blends

Wide-Angle X-ray Diffraction (WAXD) and Small-Angle X-ray Scattering analyses were carried out to evaluate the evolution of the crystalline and supermolecular structure of poly(ethylene terephthalate) (PET) blended with poly(trimethylene terephthalate) (PTT). The conditions adopted in preparing the PET/PTT 50/50 blend induce transesterification between the polyesters; these reactions produce a new molecular characteristics based on PET/PTT copolymer that exhibits its own WAXD profile. The PET/PTT 50/50 copolymers prepared by melt mixing of the homopolymers for increasing times evidence spherulitic morphology and an evolution of the crystalline structure in terms of crystallinity and crystal dimensions. The periodicity of the transesterificated samples is intermediate between the long periods observed for pure PET and pure PTT. For the PET/PTT 50/50 copolymers the value of periodicity and lamellar thickness increase with the increasing of the processing time.     

Non-isothermal Crystallization Behavior of Poly(ethylene terephthalate)/Poly(trimethylene terephthalate) Blends

Summary Non-isothermal crystallization behavior of Poly(ethylene terephthalate)/Poly(trimethylene terephthalate) blends was investigated by XRD and DSC. By XRD spectra analysis, it could be concluded that PET and PTT crystals coexisted. They did not form the cocrystals due to different chemical structures. The Avrami equations modified by Jeziorny and Ziabicki’s kinetic crystallizability analysis were employed to describe the non-isothermal crystallization process of PET/PTT blends. The results suggested that the entanglement of the two polymer chains decrease the crystallizability of PET and PTT in blend. The crystallization activation energies of the blend evaluated by the Friedman method also indicated that the presence of two components in the blends hinders the crystallization process of both components.     

Mechanical and Thermal Properties of Poly(phthalazinone biphenyl ether sulfone)/PEEK Blends

A series of blends with various compositions are prepared by melt extrusion on the basis of novel copoly(phthalazinone biphenyl ether sulfone) (PPBES) and poly(ether ether ketone) (PEEK). The melt flowability, mechanical and thermal properties of the blends are studied. The results show that the incorporated PEEK has a large influence on the melt viscosity and thermal stability of blends. The tensile strength of the blends remains at about 90 MPa at room temperature; PPBES improves the mechanical properties of PEEK at 150°C. The flexural strength and modulus of the PPBES/PEEK blends also increase with the addition of PEEK.     

Morphology,Thermal and Mechanical Properties of Poly (Styrene-Acrylonitrile) (SAN)/Clay Nanocomposites from Organic-Modified Montmorillonite

Poly (styrene-acrylonitrile) (SAN)/clay nanocomposites have successfully been prepared by melt intercalation method. The hexadecyl triphenyl phosphonium bromide (P16) and cetyl pyridium chloride (CPC) are used to modify the montmorillonite (MMT). The structure and thermal stability property of the organic modified MMT are, respectively characterized by Fourier transfer infrared (FT-IR) spectra, X-ray diffraction (XRD) and thermogravimetric analysis (TGA). The results indicate that the cationic surfactants intercalate into the gallery of MMT and the organic-modified MMT by P16 and CPC has higher thermal stability than hexadecyl trimethyl ammonium bromide (C16) modified MMT. The influences of the different organic modified MMT on the structure and properties of the SAN/clay nanocomposites are investigated by XRD, transmission electronic microscopy (TEM), high-resolution electron microscopy (HREM), TGA and dynamic mechanical analysis (DMA), respectively. The results indicate that the SAN cannot intercalate into the interlayers of the pristine MMT and results in microcomposites. However, the dispersion of the organic-modified MMT in the SAN is rather facile and the SAN nanocomposites reveal an intermediate morphology, an intercalated structure with some exfoliation and the presence of small tactoids. The thermal stability and the char residue at 700°C of the SAN/clay nanocomposites have remarkably enhancements compared with pure SAN. DMA measurements show that the silicate clays improve the storage modulus and glass transition temperature (Tg) of the SAN matrix in the nanocomposites.     

Mechanical and Thermal Properties of Flexible Poly(propylene) Composites

Summary: The melting temperature difference between poly(propylene) (PP) fibre and random poly(propylene‐co‐ethylene) (PPE) was exploited to establish processing conditions for all‐PP composite. Under these conditions, the matrix must be liquid to ensure good wetting and impregnation of fibres, though temperatures must be low enough to avoid melting of fibres. The high chemical compatibility of the two components allowed creation of strong physico‐chemical interactions, favouring strong interfacial adhesion. Static and dynamic mechanical properties and morphology of all‐PP composites were investigated according to method of preparation and compared with the behaviour of hot compacted composites, prepared under different moulding conditions. The composites were compacted with varying pressure and time, and mechanical and thermal properties of the resulting sheets were measured. With increased moulding time, more fibres melted or their original properties deteriorated. Fast cooling or quenching caused imperfect morphology. Moulding pressure played an important role. Morphology of the optimum hot compacted composite was investigated using scanning electron microscopy before and after tensile testing. Tensile fracture surfaces showed a melted phase epitaxially crystallised onto the remaining orientated phase. Compacted composites showed fibre shapes under a thin layer of PPE with all of the gaps between fibres filled by melted PPE matrix.

SEM of compacted all‐PP composite without quenching.     

PTT/PC合金的动态力学行为研究

研究了聚对苯二甲酸丙二酯(PTT)/聚碳酸酯(PC)合金的动态力学行为,探讨了增容剂环氧树脂(EP)和三元乙丙橡胶接枝甲基丙烯酸缩水甘油酯(EPDM-g-GMA)对合金动态力学行为的影响.结果表明,未增容的PTT/PC合金显示两个独立的、随配比而稍变化的玻璃化转变松弛峰Tg(PTT)和Tg(PC);PTT对PC玻璃化转变时链段运动的影响远大于PC对PTT玻璃化转变时链段运动的影响;PC能显著提高PTT的模量和热变形温度.EP强烈地影响了PTT/PC合金的松弛行为,使Tg(PTT)和Tg(PC)相互靠近,且损耗强度显著增加;当PC质量分数为30％且EP用量为2.7份时,PTT/PC合金热变形温度明显提高,高弹态平台消失,材料高温刚性增加.EPDM-g-GMA对PTT/PC合金松弛行为的影响不如EP,当EPDM-g-GMA的用量为5份以下时,仅使Tg(PTT)和Tg(PC)略有靠近,但损耗强度无明显变化,当其用量为10份时,Tg(PTT)和Tg(PC)在宽广温度区间内融合为一,损耗强度显著增加;EPDM-g-GMA使PTT/PC的玻璃态模量和高弹态模量均显著降低,但对热变形温度影响不大.     

Thermal and Mechanical Properties of Poly(Hydroxy-Imide)-Silica Nanocomposites

ABSTRACT

Thermally stable nanocomposites from polyimide (PI) and silica have been prepared through the sol-gel process. PI matrix, prepared by the reaction of a mixture of phenylenediamine and oxydianiline with an equimolar amount of pyromellitic dianhydride, acted as a reference. The polymer matrix was modified by replacing phenylenediamine with 2,4-diaminophenol to include pendant hydroxyl groups on the chain. Composite films were prepared using different amounts of silica generated in-situ in both type of matrices. These were evaluated by a variety of techniques, including FTIR, SEM, tensile, dynamic mechanical, thermal, and thermogravimetric analyses. The presence of hydroxyl group on polymer chain caused an intimate dispersion of the two phases, which resulted in the formation of nano-sized co-continuous domains as compared to that of the corresponding PI system having no pendent hydroxyl groups. The mechanical and thermal properties of these composites have been compared and explained in term of increased matrix polarity.     

Thermal properties and phase morphology of melt‐mixed poly(trimethylene terephthalate)/poly(hexamethylene isophthalamide) blends

This work examines the thermal properties and phase morphology of melt‐mixed poly(trimethylene terephthalate) (PTT)/poly(hexamethylene isophthalamide) (PA 6I) blends. Two temperatures, i.e., 250 and 260°C, are used to prepare the blends, respectively. Differential scanning calorimetry results indicate the immiscible feature of the blends. It is thus concluded that the ester‐amide interchange reaction hardly occurred in the PTT/PA 6I blends. Depending on the composition and mixing temperature, the crystallization ability of PTT in the blends is either enhanced or hindered. Basically, a lower PA 6I content shifts the PTT melt crystallization to a higher temperature, whereas a higher PA 6I content causes an opposing outcome. The original complex melting behavior of neat PTT becomes more regular after the incorporation of 60 wt % or 80 wt % of PA 6I. Thermogravimetry analyses (TGA) show that the thermal stability of the blends improves as the PA 6I content increases. The two‐phased morphology of the blends is examined by scanning electron microscopy (SEM). Polarized light microscopy (PLM) results reveal that the PTT spherulites become coarser with the inclusion of PA 6I; only smaller/dispersed crystallites are observed in the blend with 20 wt % of PTT. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

聚对苯二甲酸丙二醇酯/丙烯腈-苯乙烯-丙烯酸酯共聚物共混物的制备与性能

采用扫描电子显微镜、偏光显微镜、万能材料试验机及毛细管流变仪等对聚对苯二甲酸丙二醇酯/丙烯腈-苯乙烯-丙烯酸酯共聚物（PTT/ASA）共混物的相形态、力学性能、流变性能和热老化性能进行了研究。结果表明,PTT 和ASA具有部分相容性,当ASA含量为50 ％时,共混物中形成了双连续相;随着ASA含量的增加,共混物的断面变得更粗糙,断裂方式转变为韧性断裂,ASA的加入明显提高了共混物的缺口冲击强度,但却降低了拉伸强度;共混物熔体为假塑性流体,随着ASA含 量 增 加,熔体表观黏度升高、假塑性越明显,PTT的加工性能得到改善;PTT/ASA比PTT/丙烯腈-丁二烯-苯乙烯（ABS）共混物具有更好的耐热老化性能。