丁苯橡胶的阳离子环化

应用一氯二乙基铝和苄基氯催化剂体系进行了丁苯橡胶的阳离子环化反应。研究了反应温度、苄基氯／一氯二乙基铝比例、溶剂、原胶浓度对环化的影响。发现通过控制苄基氯／一氯二乙基铝比,可在高温（１２０℃）、高原胶浓度（２～４％ｗ／ｖ）下进行丁苯橡胶的环化,制得特性粘度较原胶有大幅度降低,可溶性无凝胶的环化丁苯胶。通过对红外光谱、＾１Ｈ－ＮＭＲ谱初步解析,证实了环化反应的发生。     

Instantaneous strain recovery elasticity and endothermic heat change in nylon-6 monofilaments and silicone rubbers

The instantaneous elastic moduli for a nylon-6 monofilament were derived on strain recoveries right after creep, stress relaxation, and rapid elongation,E _c ,E _s andE _e , respectively. It was found that during strain recoveryE _s (>E _e ) andE _e increase monotonically with increasing load,m ₁, on the sample. The extrapolated value of E_s atm ₁=0 g is almost equal to Young's modulus, 4.06 GPa. The value ofE _c also increased with increasingm ₁, and atm ₁=600 g (1.93 t cm^–2) reached about 14 GPa. The endothermic heat change right after creep, stress relaxation or rapid elongation,Q, was negligibly small. For comparison,E _s ,E _c andQ were also investigated for silicone rubber. It was found thatE _s (53.8 M Pa at the draw ratioD=1.2) decreased abruptly atD=1.3. In the range ofD=1.4–1.9,E _s was only 22.6 MPa. In the case of stress relaxation,Q increased with increasingD from 4 J mol^–1 (atD=1.2) to 56 J mol^–1 (atD=1.9). FurthermoreE _c (5.58 MPa atm ₁=133.8 g (429.4 kg cm^–2)) increased gradually with increasing m₁ and attained 16.6 MPa atm ₁=548.4 g (1.76 t cm^–2). In the case of creep,Q was in the range of 0–11.5 J mol^–1 and larger when larger loads,m ₂ were removed during the later stages of creep.Dedicated to Professor Bernhard Wunderlich on the occasion of his 65th birthdayThe author wishes to thank Mr. Keizi Igarashi and Mr. Tetsuya Yasui for helping in the experiments.     

Preparation and characterization of a homobifunctional silicone rubber membrane grafted with acrylic acid via plasma-induced graft copolymerization

Polyacrylic acid (PAA) was grafted onto the surface of silicone rubber membrane (SR) by plasma-induced graft copolymerization (PIP). Ar-plasma was used to activate the surface of SR. Also, a determination was made of the influences of plasma treatment power, pressure, time, grafted copolymerization reaction time, and monomer concentration on polymerization yield. The surface properties of SR were measured by ATR-FTIR, ESCA, and SIMS. In those analyses, the elemental composition and different carbon bindings on the surface of SR were examined by ESCA with the amount of O1s/C1s being approximately 0.7 at 60 s by Ar-plasma treatment (60 W, 200 mtorr). The peroxide group introduced on SR was measured via 1,1-diphenyl-2-picryhydrazyl (DPPH). The optimum amount of peroxide groups was 6.85 × 10⁻⁸ mol/cm² at 60 s of Ar-plasma treatment. The peroxide group (33D peak) was introduced onto the surface of SR by negative spectra of SIMS analysis after SR treatment by Ar-plasma. An increase was obtained in grafted polymerization yield with a region of 5 to 50% (v/v) of acrylic acid aqueous solution. Both sites of polyacrylic acid were detected after staining by toluidine blue O. That is, a homobifunctional membrane was developed via this surface modification method. © 1996 John Wiley & Sons, Inc.     

Structure and dynamics of MG rubber studied by dynamic mechanical analysis and solid‐state NMR

Methyl‐methacrylate‐grafted natural rubber was prepared by free radical polymerization of methyl methacrylate in natural rubber latex, and their structure and dynamics were investigated by dynamic mechanical analysis and solid‐state nuclear magnetic resonance (NMR). Samples were prepared by chemical initiation and high‐energy radiation. The changes of glass transition temperature and tan δ max with different total poly(methyl methacrylate (PMMA) content are reported. The effect of the change in composition in copolymers on tan δ peak width, tan δ max, and area under the tan δ curve are used to understand the miscibility and damping properties. Solid‐state ¹³C‐NMR measurements were carried out to determine several relaxation time parameters, such as rotating frame and laboratory frame proton and carbon relaxation times. Cross polarization times and carbon relaxation times were interpreted based on the changes in the molecular motion. Proton relaxation times were interpreted based on the heterogeneity of the matrix. Results confirmed phase separation and a presence of an interfacial region. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1141–1153, 1999     

Features of crystallization behavior of natural rubber/halloysite nanotubes composites using synchrotron wide-angle X-ray scattering

The correlation between the mechanical strength and the crystallization behavior of natural rubber (NR)/halloysite nanotubes (HNT) composites is discussed. The tensile strength of NR is improved with the addition of HNT. This improvement is attributed to the unique structure of HNT, which facilitates good dispersion and strong interfacial interaction. HNT also play an important role in assisting the strain-induced crystallization of NR. Crystallization under strain is observed using synchrotron wide-angle X-ray scattering. The stress–strain curves and the corresponding degree of crystallinity after straining provide further evidence. Based on these analyses, a mechanistic model for strain-induced crystallization and the evolution of the orientation of the network structure is proposed.     

A Closed‐Loop Control Strategy for Producing Nitrile Rubber of Uniform Chemical Composition in a Semibatch Reactor: A Simulation Study

To improve the quality of industrial nitrile rubbers, the copolymer chemical composition, p_A(t), should ideally be kept constant along the reaction. This work proposes a closed‐loop control strategy for the semibatch operation of the reactor with the aim of regulating p_A(t) within a reduced range of variability. The proposed strategy is evaluated by simulating a mathematical model of the process. To this effect, a simplified mathematical model of the reaction is first derived and then utilized to obtain a suboptimal control law and a soft‐sensor that estimates the polymerization rates. The suboptimal control law is compensated by adding a term proportional to errors in p_A(t). The simulated example considers the production of the low‐composition AJLT grade, with the copolymerization reaction represented by a detailed mathematical model adjusted to an industrial plant. Due to the high performance of the soft‐sensor, the simulation results suggest that the proposed closed‐loop strategy is efficient to adequately regulate p_A(t) in spite of structural and parametric uncertainties, while other quality variables remained practically unaffected.     

Cross‐linking and properties of rubber magnetic composites cured with different curing systems

Rubber magnetic composites were prepared by incorporation of strontium ferrite into rubber compounds based on acrylonitrile butadiene rubber and ethylene propylene diene monomer rubber. The sulfur, peroxide, and mixed sulfur/peroxide curing systems were introduced as cross‐linking agents for rubber matrices. The aim was to investigate the influence of curing system composition on curing process and cross‐link density of composite materials. Then, static and dynamic mechanical properties and thermal and magnetic characteristics were investigated in relation to the cross‐link density of rubber magnetic composites and structure of the formed cross‐links. The changes of dynamical and physicomechanical properties were in close correlation with the change of cross‐link density, whereas the tensile strength of magnetic composites showed increasing trend with increasing amount of peroxide in mixed curing systems. On the other hand, thermal conductivity and magnetic characteristics were found not to be dependent on the curing system composition.     

Stimuli‐responsive polymer nanocomposites based on styrene‐butadiene rubber and bacterial cellulose whiskers

Water‐induced mechanically adaptive rubber nanocomposites were prepared by mixing bacterial cellulose whiskers (BCWs) suspension with styrene‐butadiene rubber (SBR) latex, followed by evaporation method. The structure, morphology, dynamic mechanical properties, water stimuli‐responsive behavior, and biodegradability of SBR/BCWs nanocomposite films were investigated. The results showed that the hydrophilic whiskers had a significant reinforcement effect on the storage modulus of SBR matrix, which originated from the formation of a rigid three‐dimensional filler network within matrix by strong hydrogen bonding between whiskers. The SBR/BCWs nanocomposites showed pronounced water stimuli‐responsive behavior compared with neat SBR. The storage modulus of SBR/BCWs nanocomposite could be decreased by 99.2% after equilibrium water swelling. This remarkable water‐triggered modulus change is attributed to the disentanglement of BCWs network via competitive hydrogen bonding with water.     

Effect of high-temperature curing on the crosslink structures and dynamic mechanical properties of gum and N330-filled natural rubber vulcanizates

The effects of high-temperature curing and overcuring on the cure characteristics, crosslink structure, physical properties and dynamic mechanical properties (DMPs) of gum and carbon black (N330) filled natural rubber (NR) vulcanizates cured with conventional (CV), semi-efficient (SEV) and efficient (EV) cure systems, which have about the same total crosslink densities under a moderate curing temperature of 150°C, were investigated. The gum NR vulcanizates cured with CV, SEV and EV curing systems have about the same glass transition temperature (T_g) and tan δ values below the temperature of about 0°C, but showed some apparent differences in the tan δ values increasing in the order CVG′ and tan δ values above T_g higher than those of the gum NR vulcanizates.

High-temperature curing and overcuring cause decreases to various extents in the cure plateau torque, Shore A hardness, 300% modulus and tensile strength, and lead to apparent changes in the DMPs. Typically, there is an increase in T_g of all three kinds of gum and N330-filled NR vulcanizates because of changes in the total crosslink densities and crosslink types. The CV vulcanizates show the most significant change in cure characteristics, physical properties and DMPs since the highest content of polysulfidic crosslinks appears in the CV vulcanizate, causing the highest level of reversion and having a dominant effect on the properties.     

Measurement of bubble size distribution in protein foam fractionation column using capillary probe with photoelectric sensors

Bubble size is a key variable for predicting the ability to separate and concentrate proteins in a foam fraction ation process. It is used to characterize not only the bubble-specific interfacial a rea but also coalescence of bubbles in the foam phase. This article describes the development of a photoelectric method for measuring the bubble size distribution in both bubble and foam columns for concentrating proteins. The method uses a vacuum to withdraw a stream of gas-liquid dispersion from the bubble or foam column through a capillary tube with a funnel-shaped inlet. The resulting sample bubble cylinders are detected, and their lengths are calculated by using two pairs of infrared photoelectric sensors that are connected with a high-speed data acquisition system controlled by a microcomputer. The bubble size distributions in the bubble column 12 and 1 cm below the interface and in the foam phase 1 cm above the interface are obtained in a continuous foam fractionation process for concentrating ovalbumin. The effects of certain operating conditions such as the feed protein concentration, superficial gas velocity, liquid flow rate, and solution pH are investigated. The results may prove to be helpful in understanding the mechanisms controlling the foam fractionation of proteins.