Effect of thiophosphoryl compounds as accelerators and coupling agents on the vulcanization of NR‐XNBR blend

The effect of a number of thiophosphoryl compounds [viz., bis(isobutyl) thiophosphoryl di‐, tri‐, and tetrasulfides and bis(dicyclohexyl) thiophopsphoryl di‐, tri‐, and tetrasulfides] on natural rubber (NR)‐carboxylated nitrile rubber (XNBR) blend was studied. All these thiophosphoryl compounds are capable of forming interrubber links leading to covulcanized blends which exhibit a fair degree of synergism with respect to physical properties, the maximum being obtained at the 25% NR and 75% XNBR blend composition. This is an obvious claim that the blend under investigation is technologically compatible, having some degree of interrubber interaction which is enhanced in case of two‐stage vulcanization. The existence of interrubber interaction is judged by the swelling experiment. The blend morphology assessed by SEM micrographs corroborates the foregoing observations and accounts for the significant improvement in physical properties of the blend vulcanizates, particularly in two‐stage vulcanization. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3286‐3299, 2002     

Humidity‐sensitive properties of new polyelectrolytes based on the copolymers containing phosphonium salt and phosphine function

A simple strategy was developed based on a new reactive function‐ and a salt‐containing new monomer, 4‐vinylbenzyl dimethyl 2‐(dimethylphosphino)ethyl phosphonium chloride (VDEPC), to obtain stable humidity‐sensitive membranes. The major ingredient of a humid membrane is crosslinked polyelectrolytes obtained from copolymers of VDEPC/2‐ethylhexyl acrylate (2‐EHA) = 1/0, 4/1, and 2/1. Isothermal humidity absorption experiments were performed for the estimation of humidity‐sensing materials. The crosslinked copolymers prepared from the reaction of VDEPC/2‐EHA = 4/1 with 1,4‐dichlorobutane showed an average impedance of 595, 39.1, and 3.9 KΩ at 30, 60, and 90% RH, respectively. Their hysteresis, temperature dependence, frequency dependence, and response time were measured. The reliability including water resistance and a long‐term stability were estimated for the application of the common humidity sensor. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1062–1070, 2003     

有机硅建筑密封剂老化机理研究

本文探讨了有机硅建筑密封剂潮气固化和降解的机理，并根据理想弹性体概念和理想弹性方程及Ｍａｘｗｅｌｌ模型建立了有机硅建筑密封剂在潮气中曝露时交联和降解的动力学模型。通过实验数据求得了动力学方程。结果表明，有机硅建筑密封剂在潮气中的性能变化呈现两个不可逆的简单的一级反应，即交联反应和降解反应，这两个反应的速度常数分别为ｋ１＝０．０２２４（１／天）和ｋ２＝０．０２７（１／天）。本方程的建立，为有机硅建筑     

Toughening of vinylester–urethane hybrid resins through functionalized polymers

Liquid nitrile rubber, hyperbranched polyester, and core/shell rubber particles of various functionality, namely, vinyl, carboxyl, and epoxy, were added up to 20 wt % to a bisphenol‐A‐based vinylester–urethane hybrid (VEUH) resin to improve its toughness. The toughness was characterized by the fracture toughness (K_c) and energy (G_c) determined on compact tensile (CT) specimens at ambient temperature. Toughness improvement in VEUH was mostly achieved when the modifiers reacted with the secondary hydroxyl groups of the bismethacryloxy vinyl ester resin and with the isocyanate of the polyisocyanate compound, instead of participating in the free‐radical crosslinking via styrene copolymerization. Thus, incorporation of carboxyl‐terminated liquid nitrile rubber (CTBN) yielded the highest toughness upgrade with at least a 20 wt % modifier content. It was, however, accompanied by a reduction in both the stiffness and glass transition temperature (T_g) of the VEUH resin. Albeit functionalized (epoxy and vinyl, respectively) hyperbranched polymers were less efficient toughness modifiers than was CTBN, they showed no adverse effect on the stiffness and T_g. Use of core/shell modifiers did not result in toughness improvement. The above changes in the toughness response were traced to the morphology assessed by dynamic mechanical thermal analysis (DMTA) and fractographic inspection of the fracture surface of broken CT specimens. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 672–680, 2002; DOI 10.1002/app.10392     

Enhanced strain hardening in elongational viscosity for HDPE/crosslinked HDPE blend. I. Characteristics of crosslinked HDPE

Blending a crosslinked high‐density polyethylene (xHDPE) enhances melt strength and strain hardening behavior in elongational viscosity of high‐density polyethylene (HDPE) to a great degree. Gel fraction of xHDPE has a stronger effect on the strain hardening than sol fraction, although sol fraction also enhances the strain hardening to some degree. Further, the xHDPE crosslinked by peroxide in a compression mold exhibits more pronounced effect than xHDPE by radiation, which is attributed to the difference in the amount of the gel fraction. The xHDPE, which enhances the strain hardening, has sparse crosslink points in the network. Moreover, it was found from linear viscoelastic measurements, such as oscillatory modulus and relaxation modulus, that the xHDPE is characterized as a critical gel, which was also supported by the result of tensile testing. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 73–78, 2002     

Peroxide crosslinking of rigid poly(vinyl chloride)

The optimum conditions for crosslinking rigid poly(vinyl chloride) with trimethylolpropane trimethacrylate (TMPTMA) and peroxide have been examined. The extent of crosslinking was measured by determining gel content by Soxhlet extraction in tetrahydrofuran. Mechanical properties were measured at 130°C and dynamic viscoelastic measurements were carried out to detect changes in the glass transition temperature (T_g). It was found that 15 phr of TMPTMA and 0.3 phr of peroxide were optimum concentrations for maximizing the extent of crosslinking, tensile strength, and T_g. The lower molding temperature of 170°C was preferred to minimize thermal degradation. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2904–2909, 2007     

Exothermic effect in the process of electron‐beam curing of epoxy resins

Temperature measurements have been performed in the process of electron‐beam curing of EB‐I and EB‐II epoxy resin systems. The influence of initiator content, resin type, and dose rate on the temperature of the systems was studied. Transverse and longitudinal temperatures of samples in the glass vessel were also analyzed. The nature of temperature curves varied with the different epoxy resin systems in the steel mold, but did not change with different contents of the initiator. At the same time, the heat had no effect on the gel fraction of epoxy resin systems. The temperature curve was greatly affected by the dose rate, and its peak value, peak width, and plateau value also increased with it. The transverse temperature of EB‐II glass vessel samples increased as the radiation dose increased and, in the same sample, the temperature reduced as the distance between the radiation center and the test point increased. The longitudinal temperature of EB‐I and EB‐II resin systems in a glass vessel decreased as the radiation depth increased. As the radiation dose increased, the temperature of the EB‐I resin system increased simultaneously, while that of the EB‐II resin system initially increased and then kept constant when the dose reached a certain value. The temperatures of these two resin systems decreased rapidly when the radiation process stopped. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2217–2222, 2004     

Impact of H+ ion irradiation on Matrimid®. I. Evolution in chemical structure

Ion beam irradiation can be used to modify the structure and gas transport properties of glassy polymers. This is the first of two studies that focus on the impact of H⁺ ion irradiation on the structure and permeation properties of the polyimide Matrimid®. Specifically, the evolution in chemical structure after H⁺ irradiation over a range of fluences was analyzed using FTIR spectroscopy and dissolution studies. Although H⁺ ion irradiation at very low ion fluences induced little modification in the chemical structure, irradiation at relatively high ion fluences resulted in crosslinking of the irradiated films. The branched structure of the aliphatic methyl (CH₃) was the most sensitive to the H⁺ ion irradiation. The para‐disubstituted aromatic ring showed the strongest resistance toward ion irradiation and required fairly high doses to induce degradation. Two potential crosslinking mechanisms related to the degradation of the aliphatic methyl and the benzophenone carbonyl were presented. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2010–2019, 2003     

硅烷交联聚乙烯电缆料抗预交联添加剂的研究

研究了抑制硅烷交联聚乙烯电缆料预交联反应的方法。测试不同储存时间下的硅烷接枝聚乙烯的熔体流动速率和硅烷交联聚乙烯电缆料在挤出机中停留不同时间后挤出物的表面状况、凝胶含量等。实验结果表明,抗预交联添加剂SRA能有效地抑制硅烷接枝聚乙烯在储存和挤出加工过程中的预交联反应,提高硅烷交联聚乙烯电缆料的挤出加工性。     

Effect of crosslinkers on the preparation and properties of ETFE‐based radiation‐grafted polymer electrolyte membranes

This study concerns a comparative study of three crosslinkers, divinylbenzene (DVB), 1,2‐bis(p,p‐vinylphenyl)ethane (BVPE), and triallyl cyanurate (TAC) crosslinked poly(ethylene‐co‐tetrafluoroethylene) (ETFE)‐based radiation‐grafted membranes, which were prepared by radiation grafting of p‐methylstyrene onto ETFE films and subsequent sulfonation. The effect of the different types and contents of the crosslinkers on the grafting and sulfonation, and the properties such as water uptake, proton conductivity, and thermal/chemical stability of the resulting polymer electrolyte membranes were investigated in detail. Introducing crosslink structure into the radiation‐grafted membranes leads to a decrease in proton conductivity due to the decrease in water uptake. The thermal stability of the crosslinked radiation‐grafted membranes is also somewhat lower than that of the noncrosslinked one. However, the crosslinked radiation‐grafted membranes show significantly higher chemical stability characterized in the 3% H₂O₂ at 50°C. Among the three crosslinkers, the DVB shows a most pronounced efficiency on the crosslinking of the radiation‐grafted membranes, while the TAC has no significant influence; the BVPE is a mild and effective crosslinker, showing the moderate influence between the DVB and TAC crosslinkers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4565–4574, 2006