Preparations and properties of thermosensitive terpolymers of N‐isopropylacrylamide,sodium 2‐acrylamido‐2‐methyl‐propanesuphonate,and N‐tert‐butylacrylamide

Terpolymers based on N‐isopropylacrylamide, sodium 2‐acrylamido‐2‐methyl‐propanesulfonate, and N‐tert‐butylacrylamide were synthesized by free‐radical copolymerization with 2,2′‐azobisisobutyronitrile as an initiator. The lower critical solution temperatures (LCSTs) of the linear polymer aqueous solutions were determined by the measurement of the transmittance on UV at different temperatures. The influence of the polymer concentration, polymer composition, and ionic strength on the LCSTs of the linear polymers was investigated. The LCST decreased with increases in the hydrophobic monomer N‐tert‐butylacrylamide, polymer concentration, and ionic strength. The phase transition became sharp when the polymer concentration and ionic strength increased. Meanwhile, the crosslinked hydrogels were prepared with the same recipe used for the linear terpolymers, but a crosslinker was added to the reaction system. The swelling ratios of the hydrogels at various temperatures and salt solutions were determined. The hydrogels possessed both high swelling ratios and thermosensitivity. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

应用WCA微扰理论推算非极性液体比热容的新方法

本文首次将统计热力学的Ｗｅｅｋｓ－Ｃｈａｎｄｌｅｒ－Ａｎｄｅｒｓｏｎ（简称ＷＣＡ）微扰理论应用于非极性液体定容比热容和定压比热容的推算，用一些液体的ｐ－ｖ－Ｔ实验数据拟合了理论中所用ＬＪ势能函数的势能参数，并提出一个通用关联式。本文方法具有通用性，在编制的计算程序中只需输入物质的临界温度、临界比容、偏心因子等就能算出相应的比热容，工程应用十分方便。     

Modeling the large‐strain constitutive behavior of polycarbonate under isothermal and anisothermal conditions

The tensile behavior of polycarbonate was studied at large strains below the glass‐transition temperature. Experiments were carried out at a series of constant temperatures and also under conditions of falling temperatures. The specimens necked with a natural draw ratio of approximately 2, and the study was mainly focused on the necked material. Isothermal experiments revealed an elastic mechanism that initiated beyond the natural draw ratio. A model consisting of an Eyring process and two Gaussian elastic mechanisms was found to be applicable to both the isothermal and anisothermal stress‐relaxation and stress–strain results. The same model also produced reasonable estimates of the stresses generated during the necking process. In addition, a simple relationship between the isothermal and anisothermal stress relaxation was demonstrated. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2105–2116, 2005     

热处理前后丙烯腈／溴乙烯共聚纤维的热性能和阻燃性能研究

分析了热处理前后丙烯腈／溴乙烯共聚纤维的热性能与溴乙烯含量、升温速率或热处理时间的关系，并对纤维的阻燃性与溴含量或热处理时间关系进行了研究。结果表明，溴含量的增加或热处理时间的延长对热稳定性和阻燃性的提高有较大影响，而且经热处理后纤维的阻燃性与溴无关。     

Preparation,morphology, and mechanical properties of elastomers based on α,ω‐dihydroxy‐polydimethylsiloxane/polystyrene blends

α,ω‐Dihydroxy‐polydimethylsiloxane/polystyrene (PDMS/PS) blends were prepared by the solution polymerization of styrene (St) in the presence of α,ω ‐dihydroxy‐polydimethylsiloxane (PDMS), using toluene as solvent and benzoyl peroxide (BPO) as initiator. The PDMS/PS blends obtained by this method are a series of stable, white gums, which were vulcanized to elastomers at room temperature with methyl‐triethoxysilicane (MTES). The use level of MTES was far more than the necessary amount used to end‐link hydroxy‐terminated chains of PDMS, with the excess being hydrolyzed to crosslinked networks, which were similar to SiO₂ and acted as filler. Investigations were carried out on the elastomeric materials by extraction measurement, swelling measurement, and scanning electron microscopy. The extraction data show that at each composition the amount of soluble fraction is less than expected and the difference between experimental and theoretical values becomes more and more significant as PS content increases. This is mainly due to the grafting of PS onto PDMS and the entanglement of PS in the interpenetrating polymer network (IPN), which consists of either directly linked PDMS chains or chains linked via PS grafts and is formed by free radical crosslinking of PDMS during the radical polymerization of St. PS grafted on PDMS is insoluble and PS entangled in the IPN is difficult to extract. Both render the soluble fraction to be less than expected. As the St content in preparing PDMS/PS blends increases, the probability of grafting PS onto PDMS also increases, which may subsequently produce a higher crosslinking level of PDMS networks that linked via PS grafts by radical crosslinking. As a result, not only the amount of insoluble PS increases but also PS entangled in the IPN is more difficult to extract. Scanning electron microscopy demonstrates that the elastomer system has a microphase‐separated structure and a certain amount of PS remains in the PDMS networks after extraction, which is in accordance with the extraction data. Moreover, the mechanical properties of the elastormeric materials have been studied in detail. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3542–3548, 2004     

Composites based on eucalyptus tar pitch/castor oil polyurethane and short sisal fibers

Polymeric materials are being developed with renewable resources to promote industrial progress with environmentally friendly technologies. For this reason, polyurethane samples were prepared with 4,4′‐diphenylmethane diisocyanate (NCO/OH = 1), eucalyptus tar pitch (biopitch), castor oil as a polyol, and dibutyltin dilaurate as a catalyst. These materials were reinforced with different contents of short sisal fibers (0, 2.5, 5.0, 7.5, and 10.0%) and were prepared by resin‐transfer molding. The composites were characterized by IR absorption spectroscopy, thermal analysis (thermogravimetry and differential scanning calorimetry), impact resistance, scanning electron microscopy, and water absorption resistance. These materials showed hydrophobic characteristics, despite the addition of sisal fibers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3797–3802, 2003     

Structure and properties of polyimide‐bonded magnets processed from prepolymers based on diacetyl derivatives of aromatic diamines and dianhydrides

We report a novel method of polyimide (PI) synthesis from prepolymers based on dianhydrides and diacetyl derivatives of aromatic diamines that facilitate the preparation of a melt processable mixture at 300 ± 10°C of the prepolymer and magnetic Nd‐Fe‐B alloy to provide PI‐bonded magnets with enhanced properties. It is shown that chemical structure of the prepolymers strongly influences viscosity behavior via crystallization of the oligoimide in the melt, leading to formation of PI with rigid‐rod like structure. This structural ordering of the prepolymers based on diacetyl derivative of diamine used in this study, if not controlled, leads to exponential increase of melt viscosity with time, making it practically impossible to prepare melt processable mixture of the magnetic particles and the PI prepolymers at elevated temperatures. The results obtained demonstrate that appropriate dianhydrides and diacetyl derivatives of diamines that do not lead to crystallization of oligoimides in prepolymer mixture can be used under controlled processing conditions to prepare melt‐processable PI‐bonded magnets containing rigid‐rod like PI structure that significantly increases thermal stability of the magnets. The temperature dependencies of the magnetic properties of the PI‐bonded magnets under conditions that they are likely to encounter during their service life were found to be remarkably similar to that of commercial thermoplastic magnets such as injection‐molded nylon magnets. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 478–485, 2006     

Evaluation of Polyester Resin as a New Compatibilizer for SBR/PVC Blends

A polyester (PE) based on the glycolyzed products of PET was prepared and added in different concentrations to a series of SBR/PVC blends. The addition of the polyester showed that all properties of SBR/PVC blends were improved by incorporation of PE. Highest mechanical strength values were obtained at a polyester concentration of 7.5 phr. Thermal analysis as well as dynamic mechanical properties of SBR/PVC blends after the addition of 7.5 and 10 phr polyester indicated one single glass transition temperature. The dielectric losses (?") were analyzed in the frequency domains in the two terms of Fröhlich related to the Maxwell Wagner effect and the orientation of the aggregates caused by the movement of the main chain. The permittivity (?') values were found to increase by increasing the polyester content. This increase was followed by a decrease in the ?" up to a 7.5 phr polyester content after which no pronounced change was noticed.     

Influence of untreated and novel electron‐beam‐modified surface‐coated silica filler on the thermorheological properties of ethylene–octene copolymer

We developed surface‐modified silica fillers by coating these with an acrylate monomer, trimethylolpropane triacrylate, or a silane coupling agent, triethoxyvinyl silane, followed by electron‐beam irradiation at room temperature. These were incorporated in an ethylene–octene copolymer rubber. Thermorheological studies of the unvulcanized ethylene–octene copolymer and its untreated and modified silica‐filled composites were done with a shear dynamic oscillating rheometer. Modification of the silica filler, especially via the silanization process followed by electron beam treatment, significantly reduced filler–filler networking as revealed from the log–log plots of storage modulus and complex shear viscosity, and its real component. The rheological complexity of the compositions was analyzed from a double logarithmic plot of the storage modulus and loss modulus. The results obtained from the master curves constructed on the basis of the time–temperature superposition principle and the activation energy calculated from the Arrhenius equation for the flow of above these compounds further supported these findings. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2453–2459, 2003     

Aqueous electrochemical intercalation of bromine into graphite fibers

For the first time, graphite fibers have been electrochemically intercalated with Br⁻ that have the same structure and properties as those intercalated from vapor phase Br₂. This was accomplished by intercalating pitch-based Thornel^® K-1100 graphite fibers at low temperature (near 0 °C) and high currents (2 A) for long times (6 h). The mechanism appears to be that Br⁻ is oxidized to aqueous Br₂ which, when sufficient local concentration builds up, intercalates the fiber. This was confirmed by intercalating K-1100 fiber in a saturated aqueous Br₂ solution without passing an electrical current. The applied voltage does apparently lower the activation energy of the reaction as evidenced by the observation that P-120 and P-100 fibers will not intercalate in aqueous Br₂ unless a voltage is applied.