共聚物混溶性热力学-分子内排斥作用与附加共聚焓

基于聚合物分子间物理相互作用和统计平均场理论,引入附加共聚焓定义,使聚合物分子间的作用得到量化,同时推导出二元共混体系相互作用参数和三元共混体系混合焓关系式.利用所导出的公式解释一些常见聚合物共混体系和增溶体系.导出的关系式很好地解释了聚合物的热力学混溶性,但不能解释聚合物共混增溶作用.     

Miscibility of Solution Blends of Unsaturated Polyester Resin with Polystyrene and Polycarbonate

Miscibility studies of unsaturated polyester resin (UPR) blends with two different thermoplastics—polystyrene (PS) and polycarbonate (PC), in a common solvent, chloroform, were carried out by viscosity, ultrasonic velocity, density, and refractive index methods. Two interaction parameters, μ and α were calculated using viscosity data for these blends. The positive interaction parameter values (μ and α > 0) obtained for the UPR/PS blend and the negative interaction parameter values (μ and α < 0) obtained for the UPR/PC blend indicate that the former is a miscible blend and the latter is an immiscible blend. These results were further confirmed by the ultrasonic velocity, density, and refractive index measurements.     

Antibacterial and Miscibility Properties of Chitosan/Collagen Blends

The miscibility, bioactivity, and antibacterial properties of chitosan/collagen specimens were systematically studied. The specimens were prepared by blending collagen and chitosan with varying deacetylation degrees in solutions; the collagen molecules had been extracted from pigskins using the acid swelling-pepsin digestion method. To understand the miscibility properties of collagen and chitosan molecules, the intrinsic viscosity and differential scanning calorimetry analysis of collagen, chitosan, and collagen/chitosan specimens were performed. The instrinsic viscosity measurements suggested that chitosan and collagen molecules with varying deacetylation degrees were miscible at molecular level for all compositions and degrees of deacetylation of chitosan/collagen mixture solutions prepared in this study. Fourier transform infrared analyses suggested that the percentage of preserved triple helix structures present in collagen molecules in collagen/chitosan specimens decreased with increasing chitosan contents, since the ratios of peak absorbance at 1239 cm^?1 of amide III and 1455 cm^?1 of C?H bending of collagen/chitosan specimens decreased significantly with increase in their chitosan contents. Abnormally high denaturation temperatures (T_d) were observed as the chitosan contents of collagen/chitosan specimens reached 40 wt%, at which T_d of collagen molecules was even higher than that of the corresponding pure chitosan molecules with varying deacetylation degrees. The antibacterial activity of collagen/chitosan blends increased consistently with increasing deacetylation degrees and concentrations of chitosan molecules in collagen/chitosan solutions. Possible explanations for these interesting thermal denaturation, antibacterial, and miscibility properties of chitosan/collagen specimens are reported.     

Miscibility and Isothermal Crystallization Behavior of Poly (Butylene Succinate-co-Adipate) (PBSA)/Poly (Trimethylene Carbonate) (PTMC) Blends

Poly(butylene succinate-co-adipate) (PBSA)/poly (trimethylene carbonate) (PTMC) blend samples with different weight ratios were prepared by solution blending. The morphologies after isothermal crystallization and in the melt were observed by optical microscopy (OM). Differential scanning calorimetry (DSC) was used to characterize the isothermal crystallization kinetics and melting behaviors. According to the OM image before and after melting, it was found that the blends formed heterogenous morphologies. When the PTMC content was low (20%), PBSA formed the continuous phase, while when the PTMC contents was high (40%), PBSA formed the dispersed phase. The glass transition temperatures (T_g) of the blends were determined by DSC and the differences of the T_g values were smaller than the difference between those of pure PBSA and PTMC. In addition, the equilibrium melting points were depressed in the blends. According to these results, the PBSA/PTMC blends were determined as being partially miscible blends. The crystallization kinetics was investigated according to the Avrami equation. It was found that the incorporation of PTMC did not change the crystallization mechanism of PBSA. However, the crystallization rate decreased with the increase of PTMC contents. The change of crystallization kinetics is related with the existences of amorphous PTMC, the partial miscibility between PLLA and PTMC, and the changes of phase structures.     

Numerical simulation of thermo‐solutal‐capillary migration of a dissolving drop in a cavity

In the present paper the thermo‐solutal‐capillary migration of a dissolving liquid drop, composed by a binary mixture having a miscibility gap, injected in a closed cavity with differentially heated end walls, is studied. The main goal of the analysis is to clarify if and how the drop migration is affected by the dissolution process. The numerical code is based on a finite volume formulation. A level‐set technique is used for describing the dynamics of the interface separating the different phases. A thermodynamic constraint fixes the concentration jump between the interface sides. This jump, together with that of the concentration normal derivatives, in turn defines the entity of the dissolution cross‐flow through the interface and the interface velocity relative to the fluid. Since the jump singularity of normal derivatives cannot be easily mollified, while retaining the necessary accuracy, a scheme for the species equation is elaborated that allows sharp jumps and has subcell resolution. Steady migration speeds are determined after the start‐up phase for different radii and temperature differences. The results will be used for the preparation of a sounding rocket space experiment. Copyright © 2003 John Wiley & Sons, Ltd.     

共混聚合物辐射效应研究的进展

本文综述了近十几年来国内外共混聚合物辐射效应研究的进展情况.内容包括辐射交联理论在共混聚合物体系中的适用性、共混体系的相容性、相态结构对辐射效应的影响及共混组份间的辐射敏化及保护效应等.     

Effect of crosslinking on intermolecular interactions in thermosetting blends of epoxy resin with poly(ethylene oxide)

The miscibility and intermolecular-specific interactions in thermosetting blends of epoxy resin (ER) with poly(ethylene oxide) (PEO) cured with various amounts of 1,3,5-tridroxybenzene (THB) were investigated by differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR). The glass-transition behavior indicated that all the blends were miscible and had homogeneous amorphous phases; FTIR showed that there were the intermolecular hydrogen-bonding interactions between crosslinked ER and PEO. However, both the glass-transition behavior and infrared spectroscopy also indicated that the intermolecular interactions were significantly reduced by the formation of crosslinked structures, which was shown by comparing the experimental results of poly(hydroxyether of bisphenol A) (PH)/PEO and ER/PEO blends cured with various amounts of the curing agent. In ER/PEO blends the intermolecular hydrogen-bonding interactions were much weaker than the self-association of hydroxyls of ER, which was in marked contrast to the interactions in PH/PEO blends. In ER/PEO blends with various amounts of the curing agent, the intermolecular interactions between epoxy polymers and PEO were reduced with an increasing degree of crosslinking. The results were interpreted in terms of the effect of crosslinking on the intermolecular interactions, such as steric shielding, the screening effect, and chain connectivity resulting from the formation of the three-dimensional crosslinked network, which could reduce the intermolecular hydrogen-bonding interactions among hydroxyls of ER versus ether oxygen atoms of PEO. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2567–2575, 2004     

端羟基聚叠氮缩水甘油醚（GAP）聚氨酯力学性能的研究

采用一步法合成端羟基聚叠氮缩水甘油醚（ＧＡＰ）聚氨酯。ＤＳＣ，ＤＴＡ和静态力学性能测试结果表明：该粘合剂和硝酸酯增塑剂１，２，４－丁三醇三硝酸酯（ＢＴＴＮ）具有良好的溶混性；随硝酸酯含量的增加，聚氨酯胶片的分解峰温下降。同时观察到胶片的弹性模量和抗拉强度随交联剂含量的增加而增加，但断裂延伸率随之下降。固体填料ＨＭＸ和ＧＡＰ粘合剂之间的界面相互作用小，从而导致推进剂抗拉强度和延伸率明显降低。     

Miscibility and gas permeability of poly(ethylene-co-5,4 mol% 3,5,5-trimethylhexyl methacrylate)-polydimethyl-siloxane blends

 Blends of poly(ethylene- co-5.4 mol% 3,5,5-trimethylhexyl methacrylate) (PE-TMHM) with poly(dimethylsiloxane) (PDMS) were prepared in the PDMS content range from 0 to 20%. The miscibility was studied for PE-TMHM–PDMS blends by DSC, dynamic mechanical and microscopic spectroscopy, and the gas permeability was measured for O₂, N₂ and CO₂ as function of PDMS content. PE-TMHM and PDMS were partially miscible with each other below 20 wt% of PDMS content. The permeability coefficients (P) for O₂, N₂ and CO₂ were increased by the blending of PDMS to PE-TMHM. The change of P for O₂ with PDMS content well reflected the partially miscible phase separation behavior. Received: 10 June 1996 Accepted: 14 August 1996     

Miscibility and morphologies of poly(arylene ether phenyl phosphine oxide/sulfone) copolymer/vinyl ester resin mixtures and their cured networks

Nonreactive bisphenol A‐based poly(arylene ether triphenyl phosphine oxide/diphenyl sulfone) statistical copolymers and a poly(arylene ether triphenyl phosphine oxide) homopolymer, each having a number‐average molecular weight of about 20 kg/mol, were synthesized and solution‐blended with a commercial dimethacrylate vinyl ester resin. Free‐radical cured systems produced morphologies that were a function of both the amount of phosphonyl groups and the weight percentage of the copolymers. For example, highly hydrogen‐bonded poly(arylene ether phenyl phosphine oxide) homopolymer/vinyl ester resin mixtures were homogeneous in all proportions both before and after the formation of networks. Copolymers containing low amounts (≤30 mol %) of the phosphonyl groups displayed phase separation either before or during cure. The phase‐separated cured materials generally had phase‐inverted morphologies, such as a continuous thermoplastic copolymer phase and a particulate, discontinuous vinyl ester network phase, except for systems containing a very low copolymer content. The resin modified with a copolymer containing 30 mol % phosphine oxide comonomer showed improved fracture toughness, suggesting the importance of both phase separation and good adhesion between the thermoplastic polymer and the crosslinked vinyl ester filler phase. The results suggested that the copolymers with high amounts of phosphine oxide should be good candidates for interphase sizing materials between a vinyl ester matrix and high‐modulus carbon fibers for advanced composite systems. Copolymers with low amounts of phosphonyl groups can produce tough, vinyl ester‐reinforced plastics. The char yield increases with the concentration of bisphenol A poly(arylene ether phosphine oxide) content, suggesting enhanced fire resistance. The incorporation of thermoplastic copolymers sustains a high glass‐transition temperature but does not significantly affect the thermal degradation onset temperature. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2409–2421, 2000