Influence of Phase Morphology on Molecular Mobility of Poly(propylene)-(ethylene-vinyl acetate) Copolymer Blends

The dynamic mechanical and dielectric behaviours of Polypropylene (PP) and (Ethylene-Vinyl Acetate) Copolymer (EVA) blends are reported as a function of the morphology. For EVA contents lower than 20%, blends show the two-phase morphology characteristic of immiscible blends, with spherical EVA droplets finely dispersed in the PP matrix. After stretching in the molten state, the morphology of EVA fibers is observed. Mechanical Relaxation Spectroscopy display three relaxation processes: the EVA and PP α-relaxations associated to the glass transitions and a β-transition corresponding to a PP crystalline phase relaxation. The PP α-relaxation shifts to higher temperatures when EVA presents a fiber morphology, corresponding to a decrease of PP chain mobility since it is hindered by the reinforcement effect of EVA fibers. Quite different results are obtained by DRS analysis. In blends containing EVA fibers, only one main relaxation associated to the EVA α-transition is observed whereas one additional relaxation can be noticed in the blends containing EVA droplets. This new relaxation might be assigned to interfacial polarization effects, phenomena that are sometimes observed in heterogeneous polymer blends when a low content of one polar component is embedded in a non conductive matrix. In this case, the occurrence of a characteristic interfacial polarization relaxation appears to be correlated to the accessible experimental frequency.     

Segmental and secondary dynamics in hydrogen‐bonded poly(4‐vinylphenol)/poly(methyl methacrylate) blends

Broadband dielectric spectroscopy was used to study the segmental (α) and secondary (β) relaxations in hydrogen‐bonded poly(4‐vinylphenol)/poly(methyl methacrylate) (PVPh/PMMA) blends with PVPh concentrations of 20–80% and at temperatures from ?30 to approximately glass‐transition temperature (T_g) + 80 °C. Miscible blends were obtained by solution casting from methyl ethyl ketone solution, as confirmed by single differential scanning calorimetry T_g and single segmental relaxation process for each blend. The β relaxation of PMMA maintains similar characteristics in blends with PVPh, compared with neat PMMA. Its relaxation time and activation energy are nearly the same in all blends. Furthermore, the dielectric relaxation strength of PMMA β process in the blends is proportional to the concentration of PMMA, suggesting that blending and intermolecular hydrogen bonding do not modify the local intramolecular motion. The α process, however, represents the segmental motions of both components and becomes slower with increasing PVPh concentration because of the higher T_g. This leads to well‐defined α and β relaxations in the blends above the corresponding T_g, which cannot be reliably resolved in neat PMMA without ambiguous curve deconvolution. The PMMA β process still follows an Arrhenius temperature dependence above T_g, but with an activation energy larger than that observed below T_g because of increased relaxation amplitude. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3405–3415, 2004     

Miscibility Behaviour of Poly(ether Sulphone)/nylon-6 Blends

Binary blends of poly (ether sulphone) (PES) and Nylon-6 were prepared in a whole range of composition by melt extrusion. Miscibility behaviour of the blends were studied using thermal analytical techniques like differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). Due to the rapid crystallization of Nylon-6 as it is cooled from the melt state, its glass transition behaviour could not be detected even in the quenched samples by DSC. Furthermore, the crystallization and melting behaviour of the blends have been studied by DSC. DMA results show that the dynamic storage modulus of the blends were in-between those of the constituent polymers. Also the glass transition of Nylon-6 phase as determined by the peak in loss tangent remains constant which shows that the two polymers are immiscible. Thermal expansion coefficient of the blends as determined by TMA is greater than that of Nylon-6 signifying the increased dimensional stability of the blends at higher temperatures. Morphological studies done by scanning electron microscopy (SEM) show the biphasic nature of the blends, with clear cut boundaries between the phases because of poor interfacial adhesion. Dispersed particle size is small when Nylon-6 is the dispersed phase because of its lower melt viscosity as compared to PES. Thermal stability of the blends was measured using thermogravimetric analysis (TG). Two-step decomposition behaviour was observed because of macro-phase separated morphology. This revised version was published online in July 2006 with corrections to the Cover Date.     

聚(ε-己内酯-L-丙交酯)无规共聚物与聚乳酸共混材料的制备与性能

通过开环聚合,合成不同比例的ε-己内酯(ε-CL)与L-丙交酯(L-LA)的无规共聚物P(CL/LLA)。 将上述共聚物P(CL/LLA)与聚乳酸(PLLA)共混,制备了PLA/P(CL/LLA)共混材料。 并对其相容性、热性能、力学性能进行了研究。 结果表明,共聚物P(CL/LLA)与PLA相容性与共聚物中LA单元含量和链段的平均长度有密切关系,P(CL/LLA)中LA链段平均长度达到3.4以上时,可以与PLA很好的相互作用。 同时共聚物P(CL/LLA)中-CL-链段有很好的柔性,可以很好的改善PLLA的韧性,使PLLA材料的断裂伸长率达到500%以上。     

Synthesis and characterization of a vinyl‐terminated benzoxazine monomer and its blends with poly(ethylene oxide)

A vinyl‐terminated benzoxazine (VB‐a), which could be polymerized through ring‐opening polymerization, was synthesized through the Mannich condensation of bisphenol A, formaldehyde, and allylamine. This VB‐a monomer was then subjected to blending with poly(ethylene oxide) (PEO), followed by thermal curing, to form poly(VB‐a)/PEO blends. The specific interactions, miscibility, morphology, and thermal properties of these blends were investigated with Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry, dynamic mechanical analysis (DMA), and scanning electron microscopy (SEM). Before curing, we found that PEO was miscible with VB‐a, as evidenced by the existence of a single composition‐dependent glass transition temperature (T_g) for each composition. The FTIR spectra revealed the presence of hydrogen‐bonding interactions between the hydroxyl groups of poly(VB‐a) and the ether groups of PEO. Indeed, the ring‐opening reaction and subsequent polymerization of the benzoxazine were facilitated significantly by the presence of PEO. After curing, DMA results indicated that the 50/50 poly(VB‐a)/PEO blend exhibited two values of T_g: one broad peak appeared in the lower temperature region, whereas the other (at ca. 327 °C, in the higher temperature region) was higher than that of pristine poly(VB‐a) (301 °C). The presence of two glass transitions in the blend suggested that this blend system was only partially miscible. Moreover, SEM micrographs indicated that the poly(VB‐a)/PEO blends were heterogeneous. The volume fraction of PEO in the blends had a strong effect on the morphology. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 644–653, 2007     

Molecular Dynamics of PGA Bioabsorbable Polymer During Isothermal Cold Crystallization

An investigation was carried out on the molecular dynamics of poly(glycolide) (PGA) in its completely amorphous state and during isothermal cold crystallization. Experimental results were generated over a wide range of frequency and temperature by broad-band dielectric spectroscopy (DRS). The variation of the average relaxation time (defined as τ= ½πf_max where f_max is the frequency at maximum loss for the main α relaxation) has been studied during cold crystallization and the temperature dependence of this average relaxation time for completely amorphous and crystallized samples has been analyzed. This behaviour has been modelled by Havriliak-Negami and Vogel-Fulcher equations. The sensitiveness of the segmental dynamics to the degree of crystallinity has been analyzed, taking into account the relaxing segments and the amorphous layers between lamellae. Supporting evidence about the thermal behaviour of the polymers has been obtained with DSC. Complementarily, the evolution of the morphologies obtained during crystallization processes has been followed by optical microscopy.     

Morphology and Stress Whitening of Heterophasic Poly(propylene) Copolymer/High Density Polyethylene Blends

Summary: Effect of high density polyethylene (HDPE) addition on the morphology of heterophasic poly(propylene) copolymer (HPC) was investigated by transmission electron microscopy (TEM) and scanning electron microscopy (SEM). Stress whitening developed upon dart impact was evaluated using Gardner-type impact tester. In the TEM study of HPC/HDPE blends, a core-shell morphology was observed of HDPE encapsulated by ethylene-propylene rubber (EPR). At low HDPE weight fractions (95/5 and 90/10 HPC/HDPE), the size of dispersed phase increased compared to pure HPC. However, further increase in HDPE leads to a decrease in domain size. The impact strength reached a maximum at 90/10 HPC/HDPE blend, and then decreased with further increase in HDPE content. The stress whitening of HPC was decreased with addition of HDPE. This decrease is attributed to the difference in the shrinkage between HPC and HPC/HDPE blends. The pressure-volume-temperature relationship supports that an additional volume contraction of HDPE can reduce the stress whitening of HPC.     

The molecular dynamics of thermoreversible networks as studied by broadband dielectric spectroscopy

Polybutadienes modified by a small number of 4-phenyl-1,2,4-triazoline-3,5-dione form thermoreversible networks via hydrogen bonding between the polar stickers. The molecular dynamics of systems with different contents of polar stickers are investigated by broadband dielectric spectroscopy in the frequency regime of 10^–1–10⁹ Hz. Unmodified polybutadiene shows two relaxation processes, the -relaxation which is correlated to the dynamic glass transition of the polybutadiene, and a -relaxation corresponding to a local relaxation of polybutadiene segments. In the polar functionalized systems, besides these two relaxations, an additional relaxation process (called ^*) is observed, which occurs at lower frequencies than the -process. While the -relaxation remains unaffected by the functionalization the cooperativity of the -relaxation increases by the formation of reversible junctions and slows down considerably. This indicates a decreased mobility of the polymer matrix. At the same time the dipole moment of relaxing units contributing to the -relaxation is increased by free phenyl urazole units. The ^* is assigned to the local complex dynamics resulting from the dissociation and formation of dimeric contacts. Hence, for this dynamic process, the absolute value of the dipole moment fluctuates with time and causes a dielectric absorption. This interpretation is in agreement with the hindered reptation model of Leibler, Rubinstein and Colby and simultaneous measurements of infrared dichroism and birefringence.     

~(13)C-NMR驰豫关于星形聚环氧乙烷聚乳酸嵌段共聚物的研究

本实验测定了星形聚环氧乙烷聚乳酸嵌段共聚物(S(P)-PEO-PLA)在溶液中核磁驰豫与温度、浓度、溶剂及聚合物组成比的关系,测定了线形嵌段共聚物(L-PEO-PLA)核磁驰豫与温度、聚合物组成比的关系。实验测定了两个驰预参数T_1和η_c。采用Cole-Cole相关时间分布,log-x~2分布及Diamord Lattice模型对测定结果进行了定量解析。本文研究结果为假设的“似细胞超微~+”结构形态的存在性提供了理论依据,表明S(P)-PEO-PLA作为药物载体很有希望。     

Interaction of water in polymers: Poly(ethylene‐co‐vinyl acetate) and poly(vinyl acetate)

We studied the interaction of water in poly(ethylene‐co‐vinyl acetate) of various vinyl acetate compositions and poly(vinyl acetate), on the basis of the infrared spectrum of the water dissolved therein. The spectrum shows a very sharp and distinct band at about 3690 cm^?1 (named as A), and less‐sharp two bands around 3640 (B) and 3550 cm^?1 (C), the A band being outstanding especially at a low vinyl acetate composition. As the vinyl acetate composition increases, the A band decreases in intensity relative to the C band, whereas the B band increases contrarily. Analysis of the spectral change has elucidated that one‐bonded water (of which one OH is hydrogen‐bonded to the C?O of an ester group and the other OH is free) and two‐bonded water (each OH of which is hydrogen‐bonded to one C?O) coexist in the copolymer and that two‐bonded water increases in relative population with increasing vinyl acetate composition. Dissolved water is entirely two‐bonded in poly(vinyl acetate), in which C?O groups are densely distributed in the matrix. We proved that dissolved water in polymers is hydrogen‐bonded through one or two OH groups to the possessed functional groups but does not cluster. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 777–785, 2005     

聚醚醚酮/聚醚醚酮酮共混体系的熔融和等温结晶行为

采用熔融共混方法制备了聚醚醚酮和聚醚醚酮酮的共混物,用DSC对共混物的熔融行为和等温结晶行为进行了研究.结果表明,共混物熔点随聚醚醚酮含量增加而降低,但与聚醚醚酮酮有相同的平衡熔点,二者共混没有改变其结晶的成核与生长机制.     

Molecular weight dependence of polystyrene segmental dynamics in dilute blends with poly(vinyl methyl ether)

The segmental dynamics of backbone‐deuterated polystyrenes (d₃PS) with varying molecular weights (1.7–67 kg/mol) have been measured in blends with poly(vinyl methyl ether) (PVME). ²H NMR T₁ values at 15 and 77 MHz are reported for the pure d₃PS and for the dilute d₃PS component in PVME matrices. The temperature shift that is needed to superpose the NMR T₁ data for the pure d₃PS and the d₃PS as a dilute component in the blend ranges from 45 to 70 K. In the framework of Lodge/McLeish model, the self‐concentration value for d₃PS in these dilute blends with PVME is found to be independent of molecular weight. We thus establish for this system that the substantial influence of molecular weight on the blend segmental dynamics can be explained by homopolymer T_g differences. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2252–2262, 2007     

聚氧化乙烯/苯乙烯-马来酸钠共聚物共混体系性能研究

用热分析（DSC、TG）和FTIR对聚氧化乙烯（PEO）/苯乙烯-马来酸钠（St-alt-MANa,简称SMANa)共聚物共混体系的相容性、分子间作用、热失重等性质进行了研究。结果表明,共混物可以任意比互溶,它们之间的相互作用是PEO的醚键“-O-”和共聚物盐中的“-COOH”之间形成了氢键。TG分析结果表明,随温度的升高,首先形成了酸酐,这可由FTIR光谱确定。热降解产如CO2作为酸酐和共聚物中羧基的降解产物。与不饱和结构相关的谱带（1774cm^-1、1449cm^-1)在350℃和450℃的红外光谱中可观察到,这可能是主要的碳-碳链断裂的结果。共混体系的Tg随SMANa含量的增加而增加,而体系结果温度Tc、熔融温度Tm却略有下降,这说明两组分间具有良好的溶混性。     

PPDO/PLLA共混物的制备及其相容性

通过溶液共沉淀法制备了一系列不同组份比例的PPDO/PLLA共混物(Pw)。通过溶度参数、扫描电镜及差式扫描量热仪(DSC)研究了Pw的相容性。结果表明:PPDO与PLLA相容性差;Pw的脆断面扫描电镜图片显示,在不同共混比例下,PLLA在基体PPDO中成典型"海-岛"式分布,且当PLLA含量超过30%时,Pw中出现部分PLLA连续相。     

Reorientational Dynamics of Polyethylene Glycol/PAMAM Dendrimer Blends

The reorientational dynamics of dipoles in a series of blends of Polyethylene Glycol (PEG) and poly(amidoamine) (PAMAM) dendrimers were investigated by broadband dielectric relaxation spectroscopy (DRS). Measurements were performed over a wide range of frequency and temperature. Neat PEG exhibits three relaxation processes: the segmental process in the amorphous phase and two faster processes due to the localized motions in the amorphous regions and the rotation of hydroxyl end groups. Addition of dendrimers to the PEG matrix slows down the segmental process in the amorphous phase, but has no effect on the relaxation time of local processes in PEG. However, H-bonding which forms between the PEG oxygen and the amino groups on dendrimer surface is responsible for a shift of local processes in dendrimers to lower frequency. A detail analysis of the effect of temperature, concentration of dendrimers and molecular weight of PEG on the relaxation dynamics is offered.     

Polyamide 11/Poly(vinylidene fluoride) Blends as Novel Flexible Materials for Capacitors

A novel capacitor with high dielectric constant (ε) has been developed by blending poly(vinylidene fluoride) (PVDF) with polyamide (PA11). The blends show high dielectric constants (ε_blend = 40), which give better frequency stability (1 MHz), and excellent mechanical properties. Based on certain volume fractions, the measured dielectric constants (ε _blend ) were found to exceed those of the corresponding polymers, in contrasted to conventional composites, where ε_polymerA < ε_composite < ε_polymerB. SEM investigations suggest that the enhanced dielectric behavior originates from significant interfacial polymer‐polymer interactions. DSC and XRD demonstrate that blending PA11 with PVDF affects the crystalline behavior of each component. However, the PA11/PVDF blends exhibit a slightly high dielectric loss (tanδ ≈ 0.17), which is a great disadvantage to a capacitor. Adding a copolymer of styrene and maleic anhydride decreased the dielectric loss (tanδ ≈ 0.057) and increased the dielectric constant (ε_blend = 60). Our findings suggest that the high‐ε polymeric blends created represent a novel type of material that is flexible and easy to process, of relatively high dielectric constant, of high breakdown strength and, moreover, is suited to applications in flexible electronics.

     

聚环氧乙烷／脂肪族聚碳酸酯共混研究

本文用差热分析(DSC)和红外光谱仪(FTIR)研究了聚环氧乙烷(PEO)和新型聚合物——脂肪族聚碳酸脂(PPC)共混热行为和大分子间的相互作用。由熔点下降方法给出PEO/PPC混合体系在320K下相互作用参数为-0.46;FTIR谱表明PPC大分子链和PEO大分子链存在较强的相互作用;PEO/PPC共混形态随PPC含量增加发生了较大变化。     

Self‐assembled complexes of poly(acrylic acid) and poly(styrene)‐block‐poly(4‐vinyl pyridine)

Polymer complexes were prepared from high molecular weight poly(acrylic acid) (PAA) and poly(styrene)‐block‐poly(4‐vinyl pyridine) (PS‐b‐P4VP) in dimethyl formamide (DMF). The hydrogen bonding interactions, phase behavior, and morphology of the complexes were investigated using Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC), dynamic light scattering (DLS), atomic force microscopy (AFM), and transmission electron microscopy (TEM). In this A‐b‐B/C type block copolymer/homopolymer system, P4VP block of the block copolymer has strong intermolecular interaction with PAA which led to the formation of nanostructured micelles at various PAA concentrations. The pure PS‐b‐P4VP block copolymer showed a cylindrical rodlike morphology. Spherical micelles were observed in the complexes and the size of the micelles increased with increasing PAA concentration. The micelles are composed of hydrogen‐bonded PAA/P4VP core and non‐bonded PS corona. Finally, a model was proposed to explain the microphase morphology of complex based on the experimental results obtained. The selective swelling of the PS‐b‐P4VP block copolymer by PAA resulted in the formation of different micelles. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1192–1202, 2009