The effect of stoichiometry on chain segment and ion mobility in partially polymerized epoxy systems

The temperature dependence of steady-shear viscosity and ionic conductivity were measured for a series of unreacted mixtures and partially cured, ungelled samples of diglycidyl ether of bisphenol-A (DGEBA) and an amine cross-linking agent, diamino diphenyl sulfone (DDS). Six stoichiometric ratios of epoxide groups to amine hydrogens were examined. Free volume expressions were used to model the temperature dependence of the conductivity and viscosity for the unreacted DGEBA-DDS mixtures. In addition, these expressions were combined to successfully correlate changes in viscosity and conductivity during the DGEBA-DDS polymerization prior to gelation. It also was demonstrated that the change in weight average molecular weight during polymerization could be interpreted from the dielectric data. Through studying variations in the stoichiometry, it was possible to examine the effects of changes in chemical structure and ion concentration on the fitted parameters in the free volume models. The inherent ion transport factor (ζ₀) was found to be inversely proportional to the concentration of ions in the test samples. The fractional free volume for segmental motion (B) was found to increase with an increase in the glass transition temperature and to be a function of the rigidity of the polymer. ©1995 John Wiley & Sons, Inc.     

Rheological and dielectric changes during isothermal epoxy-amine cure

Dynamic viscosity and ionic conductivity were measured simultaneously during the cure of a digylcidyl ether of bisphenol-A (DGEBA) epoxy resin with diamino-diphenyl sulfone (DDS) by mounting a microdielectric sensor into the plates of a rheometer. Two different cure temperatures were examined. Periodically, throughout the cure, samples were removed from the plates of the rheometer, quenched, and analyzed for the glass transition temperature and epoxide conversion. The relationship between conductivity and viscosity appeared to be independent of cure temperature. A linear relation with a slope of ?1 was observed between the natural logarithms of conductivity and viscosity during the cure up to approximately 85% cure conversion. It was hypothesized that the reaction rate was hindered by diffusion at this stage in the polymerization. A free volume relationship was used to successfully correlate conductivity with viscosity up to the diffusion limited region. ©1995 John Wiley & Sons, Inc.     

MECHANICAL RELAXATION TIME OF A TWO-COMPONENT EPOXY NETWORKLiClO_4 POLYMER ELECTROLYTE

The mechanical relaxation time of a two-component epoxy network-LiClO_4 system as a polymer electrolyte was investigated. The network is composed of diglycidyl ether of polyethylene glycol (DGEPEG) and triglycidyl ether of glycerol (TGEG), wherein LiCIO_4 was incorporated and acts as both the ionic carrier and the curing catalyst. As the relaxation time is informative to the segmental mobility, which is known to be essential for ionic conductivity, the average relaxation times of the specimens were determined through master curve construction. Experimental results showed that the salt concentration, molecular weight of PEG in DGEPEG and DGEPEG/TGEG ratio have profound effect on the relaxation time of the specimen. Among these factors , the former reinforces the network chains, leading to lengthen the relaxation time, whereas the latter two are in favour of the chain flexibility and show an opposite effect. The findings was rationalized in terms of the free volume concept.     

Epoxy resins. II. The preparation,characterization, and curing of epoxy resins and their copolymers

A polymer with high aromatic ring content in the chain backbone usually has high heat and flame resistance. Three diglycidyl ethers of epoxy resins were prepared from bisphenol A (DGEBA), phenolphthalein (DGEPP), and 9,9-bis(4-hydroxyphenyl)fluorene (DGEBF) in a study of the relation between the cured polymer structure and properties. The epoxy resin prepared from phenolphthalein was separated by liquid chromatography and three fractions were obtained. The fractions had a basic structure of 3,3-disubstituted phthalide and differed only in molecular weight. The DGEPP resin changed color from yellow to red after mixing with trimethoxyboroxine (TMB), the curing agent, and to orange after completing the curing cycle. To prepare a highly crosslinked material with good thermal stability, TMB with three active Lewis sites in a molecule was used as the curing agent. The reactivity of the three different resins toward TMB, measured by differential scanning calorimetry (DSC), was DGEBA > DGEBF > DGEPP. For the same curing conditions the order of crosslink density was DGEBA > DGEPP > DGEBF. To modify the flammability of DGEBA, the conventional epoxy resin, it was copolymerized with DGEPP and DGEBF, the higher-performance epoxy resins. The glass transition temperatures of poly(DGEBA-co-DGEPP) and poly(DGEBA-co-DGEBF) systems deviated from this relationship. The DGEBF copolymers showed an increased char residue (40 wt % at 700°C) at 20 mole % of DGEBF. This deviation may be due to the lower crosslinking density of this system.     

梳状丙烯酸酯类共聚物凝胶电解质的传输性能与自由体积

用三种分子量大小不等的聚乙二醇单甲醚(PEGME)与甲基丙烯酸甲酯-马来酸酐共聚物[P(MMA-co-MAh)]反应,制备了三种支链长度不等的梳状共聚物(MMA/MAh-g-PEGME), 并以此为基体, 加入增塑剂碳酸丙烯酯(PC)和高氯酸锂(LiClO₄), 采用溶剂浇铸法制备了三种凝胶聚合物电解质(GPE)膜, 研究了其离子传输性能, 发现该聚合物凝胶电解质的离子传输机理符合VTF (Vogel-Tamman-Fulcher)方程, 即离子传输性能与凝胶体系自由体积的大小有关; 采用正电子湮没寿命谱仪(PALS)研究了GPE 体系的自由体积特性, 获得了各支链长度不同的共聚物凝胶电解质的自由体积分数, 分析各自由体积与离子传输性能之间的关系, 建立了共聚物结构、凝胶聚合物自由体积及其传输性能之间的关系. 发现梳状共聚物支链长度越长, 凝胶电解质的自由体积越大, 离子传输性能越高.     

Viscoelasticity of rubber-resin mixtures

The dynamic viscoelastic response of blends in various proportions of natural rubber with each of two tackifier resins, a poly(β-pinene) and a pentaerythritol ester of hydrogenated rosin, has been investigated. Results are presented in the form of master curves of the modulus G′_r and the viscosity η′_r against frequency. The two resins show remarkably similar behavior in modifying the viscoelastic behavior of the rubber; the most obvious effects of increasing resin concentration are (a) a displacement of the transition zone toward lower frequencies, (b) a reduction in width and eventual elimination of the “rubbery plateau,” and (c) a displacement of the terminal zone in the direction of higher frequencies. The effect (a) is interpreted in molecular terms as a restriction of segmental motion and may be quantitatively evaluated in terms of reduced fractional free volume and increased monomeric friction coefficient. Effects (b) and (c) are explicable in terms of reduced average molecular weight, with consequent reduction in entanglement coupling and resistance to viscous flow. Quantitative analysis of the results, using relaxation time spectra, lends support to the iso-free-volume theory of the glassy state and shows a correlation between fractional free volume and monomeric friction coefficient.     

Study of the γ-alumina polymerization of furfuryl alcohol

The γ-alumina polymerization of furfuryl alcohol produces a polymer differing in structure from that obtained by polymerization with acid catalysts. In order to gain a better understanding of the basic chemistry of this method of polymerization furfuryl alcohol, studies were done, both with γ-alumina-polymerized and acid-polymerized furfuryl alcohol resins, concerning both the chemical nature of the resin constituents, and the manner in which these constituents affect resin molecular size distribution as measured by gel permeation chromatography. Because of numerous side reactions, the γ-alumina polymerization of furfuryl alcohol was found to result in the early elimination of many of the molecules containing functional groups necessary to the sustenance of polymerization. As a consequence even at advanced degrees of polymerization there remain relatively large amounts of low molecular weight components that have not further polymerized. At the higher degrees of polymerization, the high molecular weight end of the resin molecular size distribution was observed to be significantly enhanced over that of the acid-polymerized resins. The latter behavior is attributed to the occurrence of crosslinking reactions made possible by the higher temperature required for polymerization with γ-alumina. It is further concluded that the curing processes of γ-alumina-polymerized furfuryl alcohol resins proceed by a mechanism unlike that of the acid-polymerized resins.     

Organic/inorganic hybrid epoxy nanocomposites based on octa(aminophenyl)silsesquioxane

Octa(aminophenyl)silsesquioxane (OAPS) was used as the curing agent of diglycidyl ether of bisphenol-A (DGEBA) epoxy resin. A study on comparison of DGEBA/OAPS with DGEBA/4,4′-diaminodiphenyl sulfone (DDS) epoxy resins was achieved. Differential scanning calorimetry was used to investigate the curing reaction and its kinetics, and the glass transition of DGEBA/OAPS. Thermogravimetric analysis was used to investigate thermal decomposition of the two kinds of epoxy resins. The reactions between amino groups and epoxy groups were investigated using Fourier transform infrared spectroscopy. Scanning electron microscopy was used to observe morphology of the two epoxy resins. The results indicated that OAPS had very good compatibility with DGEBA in molecular level, and could form a transparent DGEBA/OAPS resin. The curing reaction of the DGEBA/OAPS prepolymer could occur under low temperatures compared with DGEBA/DDS. The DGEBA/OAPS resin didn’t exhibit glass transition, but the DGEBA/DDS did, which meant that the large cage structure of OAPS limited the motion of chains between the cross-linking points. Measurements of the contact angle indicated that the DGEBA/OAPS showed larger angles with water than the DGEBA/DDS resin. Thermogravimetric analysis indicated that the incorporation of OAPS into epoxy system resulted in low mass loss rate and high char yield, but its initial decomposition temperature seemed to be lowered.     

Dielectric properties of bisphenol-a epoxy resins

The α-relaxation process of seven commercial diglycidyl ether of bisphenol-A (DGEBA) epoxy resins of varying molecular weights, without hardener, was characterized by measuring the frequency and temperature dependence of the complex permittivity, (?ast;). The temperature dependences of the frequency of maximum dipole loss ?_max and the ionic conductivity σ are non-Arrhenius and can be described by the Williams-Landel-Ferry (WLF) equation. The frequency dependence of the molecular relaxation process is described by the Kohlrausch-Williams-Watts (KWW) relaxation function. The WLF C₁ parameter and the KWW β parameter, describing the temperature and frequency dependences, respectively, vary systematically with the molecular weight of the resin. These results are discussed in the context of recent theories of the glass transition.     

Study of viscosity behavior and retanning properties of sulfonated glutaric dihydrazide formaldehyde condensate under different reactant ratios

Sulfonated glutaric dihydrazide formaldehyde condensates with less than 0.05% free formaldehyde were prepared through controlled reaction of glutaric dihydrazide, sodium metabisulfite, and formaldehyde in three processing steps. Mole ratio of sodium metabisulfite/glutaric dihydrazide (S/GDH) was varied from 0.1 to 0.5 and that of formaldehyde/glutaric dihydrazide (F/GDH) from 1 to 3. The effects on viscosity and fluidity of resins were observed with varying degrees of sulfonation and changeable mole ratio of formaldehyde/glutaric dihydrazide. Viscosity of resins showed increasing trend with increasing mole ratio of formaldehyde/glutaric dihydrazide and decreasing trend with increasing mole ratio of sodium metabisulfite/glutaric dihydrazide. Increase in viscosity of resins was due to increase in molecular weight of polymer chains. After gaining a critical molecular weight during condensation, resins turned into gel form. The resins were comparatively applied on chrome tanned cow hide against commercial sulfonated urea formaldehyde powder resin (Resin UFT).     

Prediction and estimation of solvent diffusivities in polyacrylate and polymethacrylates

The relationship between polymer side‐chain length and the hole free volume that is effective for solvent diffusion was investigated for polyacrylates and polymethacrylates on the basis of free‐volume theory. Measurements of a polymer's viscoelasticity and solvent diffusivity provided experimental evidence for polymer segment mobility, and the results indicated that hole free volume in a linear polymer increases with hydrocarbon side‐chain length. Because the molecular mechanisms of polymer viscoelasticity and diffusivity are identical, the free‐volume parameters obtained for polyacrylates and polymethacrylates by measuring the polymer viscoelastic‐temperature dependence can reliably be used in predicting the solvent diffusion coefficient. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1393–1400, 2003     

离子液体催化改质稠油实验研究

研究了离子液体对稠油黏度、组成和平均分子量的影响。结果表明,离子液体对稠油具有较好的改质降黏作用。稠油经离子液体处理后,其饱和烃、芳香烃、胶质质量分数增加,沥青质质量分数明显下降,从而导致稠油的黏度降低,平均分子量减小。研究结果还表明,过渡金属盐改性离子液体对稠油的改质具有催化作用。     

Effect of matrix chain length on the electrophoretic mobility of large linear and branched DNA in polymer solutions

We study the effect of matrix chain molecular weight Mw and concentration c on the electrophoretic mobility micro of large linear and star-like, branched DNA in polymer solutions. Polyethylene oxide (PEO) with narrow molecular weight distributions form the main focus of this study. For PEO concentrations ranging from one half the overlap concentration, c*, to 3c*, the effective drag coefficient, zeta is identical with (mu0/mu) - 1, satisfies the following approximate scaling relationship, zeta approximately cMw(0.7). Here, mu0 is the electrophoretic mobility in free solution. While the concentration dependence is consistent with predictions from the transient entanglement coupling (TEC) model, the molecular weight dependence is significantly weaker. Although a similar dependence of mobility on Mw can be predicted when nonentangling collisions are the dominant source of drag, a model based on these collisions alone cannot reproduce the experimental observations. We also find that the architecture of large DNA does not affect either the concentration dependence or molecular weight dependence of the electrophoretic mobility.     

共聚结构和分子量对热塑性聚酰亚胺树脂熔融与耐热性能的影响

基于具有刚性主链结构的4,4'-(六氟亚异丙基)双邻苯二甲酸酐/对苯二胺(6FDA/p-PDA)树脂体系, 通过共聚引入间苯二胺(m-PDA)、 4,4'-二氨基-2,2'-双三氟甲基联苯(TFDB)和9,9'-双(4-氨基苯基)芴(BAFL)等主链刚性且兼具大自由体积特性的芳香二胺, 以非反应性封端剂邻苯二甲酸酐(PA)对分子量进行调控, 设计制备了系列分子量可控的热塑性聚酰亚胺(TPI)树脂. 系统研究了共聚结构和分子量对TPI树脂熔融性能和耐热性能的影响, 构建了聚合物的聚集态结构与树脂熔融性能的对应关系, 并对树脂的室温和高温力学性能进行了评价. 研究结果表明, 大自由体积的芳香二胺共聚结构的引入可有效降低分子链堆砌密度, 增大聚合物的自由体积, 从而赋予树脂良好的熔融性能. 降低设计分子量可进一步改善树脂的熔融加工性. 这类具有刚性主链结构的TPI树脂兼具优异的耐热性能和力学性能, 树脂的玻璃化转变温度在308~338 ℃之间, 以TFDB和BAFL共聚制备的TPI-C-25K和TPI-D-25K树脂表现出高强高韧的特性, 拉伸和弯曲强度分别超过120 MPa和190 MPa, 断裂伸长率大于8.2%, 并且在250 ℃高温下表现出良好的耐热稳定性.     

Effect of macro-RAFT agent on the morphology of polymer dispersed liquid crystals

In this study, macro-(RAFT) reversible additional fragmental chain transfer agent prepared by reversible additional fragmental chain transfer polymerisation has been incorporated into polymer dispersed liquid crystals (PDLCs). The effects of concentration, molecular weight and glass transition temperature of macro-RAFT agent were studied in terms of morphology, polymerisation kinetics, molecular weight of polymer matrix and electro-optical properties of the films. It was found that the key factor influencing morphology was the mobility of macro-RAFT agent chain rather than polymerisation rate and molecular weight of polymer matrix. Furthermore, the decrease in the mobility of macro-RAFT agent chain caused less liquid crystal nematic fraction, smaller liquid crystal domain size and greater driving voltage.     

Preparation and properties of aniline chain-extended thermoplastic epoxy resin using triphenylphosphine as catalyst

Thermoplastic resins have been widely used in fiber reinforced polymer composites because of its recyclability and short cycle times. However, the high viscosity after heating and melting restricts its infiltration on the surface of fiber. In this study, a series of thermoplastic epoxy resins were prepared via the chain extension reaction of epoxy groups with liquid aniline using triphenylphosphine (TPP) as catalyst. The relationship between polymer network structure and performance was comprehensively investigated. The solubility tests indicated that excessive aniline or TPP facilitated the crosslinking of resins. Besides, on the premise of thermoplasticity, appropriate TPP could increase the degree of chain extension, molecular weight, and glass transition temperature of resins. Furthermore, the in-situ polymerization process facilitated infiltration between epoxy resin and the fibers before chain extension reaction. The bending test showed that the flexural performance of the sample with 2 phr of TPP was improved by 38.8%. Therefore, this work provides a feasible method to prepare the thermoplastic epoxy resins and its fiber-reinforced composites with good mechanical properties.     

Gamma radiation-initiated polymerization of styrene at high pressure. II. Chain termination

The pressure dependence of the termination rate constant k_t for the free radical polymerization of monomers such as styrene is a function of polymer chain length, chain stiffness, and monomer viscosity, all of which influence the rate of segmental diffusion of an active radical chain end out of the coiled polymer chain to a position in which it can react with a proximate radical. Although k_t is not sensitive to changes in chain length, the large increase in molecular weight is responsible for a significant reduction in k_t at high pressures. For most of the common vinyl polymers, which exhibit some degree of chain stiffness, k_t is inversely proportional to a fractional power of the monomer viscosity because it depends in part on the resistance of chain segments to movement and in part on the influence of viscosity in controlling diffusion of the chain ends. The fractional exponent appears to increase with pressure and this is interpreted as evidence that the polymer chains become more flexible in a more viscous solvent. Because the fractional exponent is higher for more flexible chains, the value of the activation volume for chain termination is an indication of the degree of flexibility of the polymer chains, provided that the monomer is a good solvent for the polymer and that chain transfer is negligible.     

Molecular dynamics simulation of the polymer electrolyte poly(ethylene oxide)/LiClO(4). II. Dynamical properties

The dynamical properties of the polymer electrolyte poly(ethylene oxide) (PEO)LiClO(4) have been investigated by molecular dynamics simulations. The effect of changing salt concentration and temperature was evaluated on several time correlation functions. Ionic displacements projected on different directions reveal anisotropy in short-time (rattling) and long-time (diffusive) dynamics of Li(+) cations. It is shown that ionic mobility is coupled to the segmental motion of the polymeric chain. Structural relaxation is probed by the intermediate scattering function F(k,t) at several wave vectors. Good agreement was found between calculated and experimental F(k,t) for pure PEO. A remarkable slowing down of polymer relaxation is observed upon addition of the salt. The ionic conductivity estimated by the Nernst-Einstein equation is approximately ten times higher than the actual conductivity calculated by the time correlation function of charge current.     

A free-volume-based approach to modeling thermoset cure behavior

The free-volume theory for the temperature dependence of transport properties of glass-forming polymers is extended to obtain their relationship to the extent of cure. This treatment centers on the unifying role of molecular mobility and yields a model which connects extent of reaction, viscosity, diffusivity, ionic conductivity and dipole relaxation time. The temporal dependence of these properties is expressed by coupling the extended free-volume model with a relationship for the rate of cure, which included diffusional limitations. Analyses based on this model are applied to the observed behavior of a model epoxy-amine resin system. The intrinsic kinetics of this model system are shown to be first order. It is shown that diffusional limitations strongly affected the progress of the reaction in the final stages of cure. The diffusion-modified rate expression predictions agree with extent of reaction versus time data over the range of experimental temperatures. The temporal dependence of viscous behavior of the curing resin is measured. The extended free-volume model accurately describes the evolution of resin viscosity during cure. The dielectric behavior is similarly characterized and is in close agreement with the predictions of the general free-volume expression. The results of this study indicate that the free-volume theory modified to account for molecular weight effects allows prediction of resin properties with a two-parameter model. The results show that a power-law relationship exists between viscosity and ionic conductivity. This result suggests that electrical properties may be used for on-line measurement of resin viscosity during cure.     

Positron annihilation in ionic conductivity polymers

Positron annihilation lifetime spectra and ionic conductivity have been measured for poly(etherurethane)-LiClO₄ as a function of temperature. The effects of Li salt on glas transition free volume and ionic conductivity have been discussed. A correlation between fractional free volume and ionic conductivity was first experimentally confirmed by using the free volume theory.Supported by the National Natural Science Foundation of China.