1. Vulcanization accelerators change all parameters of the kinetic strength curve during the vulcanization of natural-rubber mixtures with low sulfur contents. 2. Calculation of the kinetic constants of the fundamental vulcanization equation proposed by Dogadkin, Karmin, and Gol'berg shows that vulcanization accelerators affect both the kinetics of the interaction of rubber with sulfur and the kinetics of the interaction of rubber with oxygen. 3. Direct experiments on the oxidation of rubber have shown that tetramethylthiuram disulfide and diphenylguanidine retard the process of addition of oxygen to rubber, while mercaptobenzothiazole accelerates this process. 4. Data on the rate of plasticization and change in viscosity of rubber solutions during oxidation indicate that tetramethylthiuram disulfide and diphenylguanidine promote the disintegration of molecular chains of rubber during the oxidative destruction of the latter. 5. The activation energy of the process of oxidation of rubber in the presence of mercaptobenzothiazole corresponds to the activation energy calculated from the fundamental vulcanization reaction for the process of oxidative destruction. This provides additional proof of the participation of oxygen in the vulcanization process. 6. It has been established with the aid of the methyl iodide reaction that accelerators increase the bridge-sulfur content of the vulcanizate, which is present in the form of monosulfides, with one sulfur atom connected to an allyl type radical. 7. With increasing temperature, the tensile strength at the vulcanization optimum increases in mixtures containing tetramethylthiuram disulfide, decreases in mixtures containing mercaptobenzothiazole, and remains unchanged in mixtures containing diphenylguanidine. The limiting strength decreases in all cases with increasing temperature. This phenomenon is explained on the basis of the proposed concepts of the character of vulcanization kinetics and of the nature of the vulcanization optimum.
The fundamental process of vulcanization consists in the combination of rubber with a vulcanizing agent : sulfur, sulfur monochloride, etc. The kinetics of this process may be expressed by monotonous curves. These may be interpreted either as the result of the heterogeneous character of the reaction or as the result of the combination of several homogeneous reactions. At the same time that the rubber combines with the vulcanizing agent, and largely as a consequence of this, a number of its physical-chemical and mechanical properties—solubility, density, tensile strength and other properties—undergo a change. These changes are extremely interesting from the technological point of view. In distinction to the kinetics of the combination of rubber with the vulcanizing agent, the kinetics of these processes can in most cases be represented by curves with a maximum or minimum. Thus, in the vulcanization of crude rubber, the tensile strength and modulus change according to a curve having a maximum; the solubility change follows a curve with a minimum. This character of the change experienced by the principal technical properties of the rubber determines the so-called “vulcanization optimum”. This term refers to that moment in the process of vulcanization when the particular property attains the necessary maximum or minimum, depending on the technical purposes of the vulcanizate.
1. The kinetics of the plasticization of a butadiene-styrene copolymer on a cold laboratory mill was studied. It was established that, at temperatures of 20–30° C, the plasticity rises steadily and that, consequently, under these conditions a monodirectional destructive process takes place. 2. The kinetics of plasticization of a butadiene-styrene copolymer was investigated in a laboratory banbury at 140° C, both with and without a plasticization aid (chemical). Plasticization at a high temperature is accompanied by the simultaneous operation of the two reactions of destruction and structure formation proceeding at cross-purposes, and may be described by a kinetic equation of the type: P=P0 (1+a⋅m)(1−b⋅n) 3. Plasticized rubbers obtained by breakdown on a cold mill have a smaller capacity for recovery than those obtained by treatment in a boiler or a banbury at temperatures above 120° C. 4. Plasticized rubbers obtained by milling on a cold mill give stocks with higher tensile strength and higher relative elongation than rubbers plasticized by hot treatment. 5. The high recovery capacity of rubbers plasticized at elevated temperatures and the lowering of the physical and mechanical properties of vulcanizates of those rubbers are explained by the branched molecules which they form during structure formation.
Years of research at the S. V. Lebedev All-Union Scientific Research Institute for Synthetic Rubber have provided industry with a number of methods for making synthetic rubber from isoprene. Of all the known synthetic rubbers this comes closest to natural rubber in structure and properties; it is the best available substitute of natural rubber, possessing a high degree of elasticity and strength. The present article is a brief summary of the basic work on isoprene rubber done by the Scientific Research Institute of the Tire Industry. On the basis of this work recommendations were made for the development of the production of synthetic isoprene rubber and the substitution of isoprene rubber for natural rubber in the manufacture of heavy duty truck tires. By using different polymerization processes it is possible to produce isoprene rubbers whose chain structures are very similar, but whose molecular weights, and therefore physical and technological properties, are very different. The cis structure of the 1,4 polyisoprene chains is the basic structural element of the new isoprene polymer. Therefore these synthetic isoprene rubbers (SKI) obtained through catalytic polymerization when vulcanized show a crystalline structure when x-rayed in the stretched state. The x-ray photographs also show that the geometric distribution of interference spots in SKI rubbers corresponds to the distribution of interference spots in natural rubber, but that the relative intensities of the crystalline, liquid, and amorphous scatterings in the two rubbers are different (Figure 1).
1. It is shown that the tensile strength of vulcanized butadiene-styrene rubber is a linear function of the plasticity of the original material. 2. Proceeding from concepts of the presence during vulcanization of a number of opposing processes of structure formation and destruction, both of which influence the molecular weight of the rubber, a general equation is derived which expresses the kinetics of the change of tensile strength of a vulcanizate. 3. Experimental material is offered which proves the applicability of the proposed equation to the representation of the kinetics of vulcanization of mixtures of natural rubber containing relatively small sulfur contents, i.e., up to 3 per cent.
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