Vulcanization of Elastomers. 39. Vulcanization of Natural and Synthetic Rubbers by Sulfur and Sulfenamides. II

1965 ◽  
Vol 38 (1) ◽  
pp. 176-188 ◽  
Author(s):  
W. Scheele ◽  
G. Kerrutt
Keyword(s):  
Natural Rubber ◽  
Concentration Dependence ◽  
Intermediate Compound ◽  
Kcal Mole ◽  
Experimental Conditions ◽  
Molar Ratios ◽  
Induction Periods ◽  
Induction Times ◽  
Kinetics Of ◽  
Kinetics Of Vulcanization

Abstract The dependence of the kinetics of vulcanization of natural rubber by sulfur in presence of N-cyclohexyl-benzothiazolylsulfenamide (CHBS) on temperature and for varied molar ratios of accelerator and sulfur was more exactly investigated. 1. Although the vulcanization of natural rubber accelerated with N-cyclohexyl-benzothiazolylsulfenamide with conventional experimental conditions is characterized by very long induction times, nevertheless—as also for other accelerated vulcanization reactions—sulfur decrease follows a time law with nt<1 and the activation energy, as in other cases, is calculated to be 29 kcal/mole. 2. The value nt=0.6 is found for the exponent of the time law, independent of temperature and concentration of reactants. 3. The concentration dependence of the rate of sulfur decrease under conditions of constant sulfur content and increasing sulfenamide concentration is found to be consistent with catalysis by an intermediate compound. 4. The actual accelerator may be essentially cyclohexylammonium-benzothiazoylmercaptide. 5. The temperature and concentration dependence of the induction periods for sulfur decrease and crosslinking were investigated. The course of crosslinking with reaction time, which is characterized by strong reversion, is discussed.

Vulcanization of Elastomers. 40. Vulcanization of Natural Rubber and Synthetic Rubber with Sulfur in Presence of Sulfenamides. III

1965 ◽  
Vol 38 (1) ◽  
pp. 189-203 ◽  
Author(s):  
W. Scheele ◽  
J. Helberg
Keyword(s):  
Activation Energy ◽  
Reaction Mechanism ◽  
Natural Rubber ◽  
Rate Constants ◽  
Sulfur Concentration ◽  
Kcal Mole ◽  
Synthetic Rubber ◽  
Chemical Constitution ◽  
Induction Times ◽  
Kinetics Of

Abstract Vulcanization of natural rubber with sulfur was studied in presence of six sulfenamides, to determine the effect of the chemical constitution of the sulfenamide on sulfur decrease and on crosslinking. The results can be condensed as follows: (1) The kinetics of sulfur disappearance is in every respect qualitatively independent of the chemical constitution of the sulfenamide. (2) For the sulfenamides investigated, the smallest and largest rate constants for sulfur decrease differed only by a factor of two. (3) Greater differences are encountered in the induction times for sulfur decrease and for crosslinking. The latter are notably longer than those for sulfur disappearance. (4) The same activation energy, 23 kcal/mole, is derived from the temperature dependence of the induction times for all the sulfenamides. (5) The dissociation of sulfenamides in solution and their reaction with mercaptobenzothiazole were investigated further. The results provide the basis for a proposed reaction mechanism, which is presented in detail and can account for a number of the features typical of sulfenamide-accelerated vulcanization. (6) The drop in sulfur concentration goes at practically the same rate, if one introduces, instead of N, N-dicyclohexyl-2-benzothiazolesulfenamide, the corresponding ammonium mercaptide in equimolar concentration.

Vulcanization of Elastomers. 36. Vulcanization of Natural Rubber and Synthetic Rubbers with Sulfur in Absence of Accelerators. II

1964 ◽  
Vol 37 (4) ◽  
pp. 910-926 ◽  
Author(s):  
W. Scheele ◽  
H. Müller ◽  
W. Schulze
Keyword(s):  
Natural Rubber ◽  
Concentration Dependence ◽  
Good Description ◽  
Kcal Mole ◽  
First Order ◽  
Different Temperatures ◽  
In Cis ◽  
Kinetics Of ◽  
Limiting Value ◽  
Homolytic Dissociation

Abstract In continuation of earlier work with natural rubber, the kinetics of sulfur decrease were studied in certain synthetic rubbers for different temperatures and sulfur concentrations. At the same time the formation of polysulfide bound sulfur was studied, using as example the reaction of sulfur with natural rubber and synthetic rubbers. It was found that: 1) When the decrease in sulfur concentration is portrayed by curves which are convex to the time axis (Perbunan), the 0.6th order time-law is fulfilled, (as in the case of natural rubber independent of temperature and concentration. 2) In contrast, the concentration dependence of the rate at which sulfur decreases, both in Perbunan and cis 1,4-polybutadiene, denotes a first-order reaction in agreement with experience with natural rubber. 3) The activation energy of sulfur decrease has the same magnitude for all the elastomers investigated (34 to 36 kcal/mole). 4) The disagreement between the time law and the concentration dependence of the rate of sulfur disappearance encountered in all the experiments with 1,5-polyenes, is interpreted as indicating autocatalysis, which likewise explains the shape of the curves for sulfur disappearance. 5) Sulfur reacts considerably faster in natural rubber and Perbunan than in cis 1,4-polybutadiene; consequently a homolytic dissociation of the S8-ring cannot be rate-determining. 6) Polysulfide sulfur shows, in each case, a maximum with reaction time, and in completely reacted vulcanizates it tends toward a limiting value. An equation was found, which provides a good description of change with time of polysulfide concentration (natural rubber and cis 1,4-polybutadiene). 7) An explanation is given for the appearance of the polysulfide maximum; and how the reaction of sulfur with 1,5-polyenes can be represented, making use of all available results, is discussed.

Copolymerization of Isobutene and Isoprene at “High” Temperature with Syncatalyst Systems Based on Aluminum Organic Compounds

1976 ◽  
Vol 49 (4) ◽  
pp. 937-959 ◽  
Author(s):  
S. Cesca ◽  
M. Bruzzone ◽  
A. Priola ◽  
G. Ferraris ◽  
P. Giusti
Keyword(s):  
Energy Savings ◽  
Ion Pairs ◽  
Great Part ◽  
Methyl Chloride ◽  
Reactivity Ratio ◽  
Experimental Conditions ◽  
Noticeable Increase ◽  
Catalyst Systems ◽  
Kinetics Of ◽  
Kinetics Of Vulcanization

Abstract New catalyst systems based on alkylaluminum derivatives and halogen or interhalogen compounds were found highly efficient in the synthesis of high-molecular-weight IIR at temperatures above − 50°C. The reaction mechanism was studied in detail for the system Et2AlCl + Cl2. The reactions occurring between chlorine, isobutene, Et2AlCl, and the solvent (CH3Cl) were elucidated and studied under various experimental conditions (e.g. presence or absence of light, simultaneous presence of the copolymerization system components, temperature, type of halogen, use of model compound of isobutene). It was concluded that halogenium ions, i.e. Cl+, Br+, or I+, are the initiating species. Kinetic and conductometric investigations showed that scarcely dissociated ion pairs, e.g. Cl+[Et2AlCl2]−, were formed in the absence of monomer; but in the presence of isobutene, a noticeable increase of the electrical conductivity and rapid polymerization occurred. The maximum polymerization rate was first order with respect to the concentrations of monomer, Cl2, and Et2AlCl. In the homopolymerization of isobutene, transfer to monomer and termination reactions were negligible. The MW of IIR was found to be mainly dependent on the concentrations of the catalyst components, on isoprene concentration, and on temperature. The reactivity ratio of isobutene with isoprene was found to be r1=2.5±0.5 at −35°C, while the activation energies relative to MW were −5.8 ± 0.4, kcal/mol for polyisobutene, and −5.7 ± 0.7 and − 4.3 ± 0.5 kcal/mol for IIR containing, respectively, 1.3 and 1.9 mol% of isoprene. The evaluation of some physicochemical and technological properties of typical IIR produced with the system Et2AlCl + Cl2, indicated that isoprene is randomly distributed along the chains and that the MWD is monomodal, while the glass transition temperature, tensile properties, mechanical-dynamic spectra, and kinetics of vulcanization are very similar to those of commercial IIR. Very preliminary data, referring to several classes of new catalyst systems yielding IIR having good properties, were also obtained. The syncatalyst systems here described can work in a homogeneous phase consisting of an aliphatic hydrocarbon besides methyl chloride, still giving IIR with high MW. Therefore, a completely homogeneous process can be envisioned for the synthesis of IIR at −50°C thus avoiding a great part of the fouling problems of the slurry process. The economic advantage of using “high” temperatures of polymerization is briefly discussed in terms of energy savings.

Vulcanization of Elastomers. 23. The Chemical Kinetics of Vulcanization Reactions and The Physical Properties of The Vulcanizates. I

1960 ◽  
Vol 33 (2) ◽  
pp. 335-341
Author(s):  
Walter Scheele ◽  
Karl-Heinz Hillmer
Keyword(s):  
Activation Energy ◽  
Physical Properties ◽  
Chemical Kinetics ◽  
Kcal Mole ◽  
First Order ◽  
Equilibrium Swelling ◽  
Kinetics Of ◽  
Kinetics Of Vulcanization ◽  
Limiting Value ◽  
Good Agreement

Abstract As a complement to earlier investigations, and in order to examine more closely the connection between the chemical kinetics and the changes with vulcanization time of the physical properties in the case of vulcanization reactions, we used thiuram vulcanizations as an example, and concerned ourselves with the dependence of stress values (moduli) at different degrees of elongation and different vulcanization temperatures. We found: 1. Stress values attain a limiting value, dependent on the degree of elongation, but independent of the vulcanization temperature at constant elongation. 2. The rise in stress values with the vulcanization time is characterized by an initial delay, which, however, is practically nonexistent at higher temperatures. 3. The kinetics of the increase in stress values with vulcanization time are both qualitatively and quantitatively in accord with the dependence of the reciprocal equilibrium swelling on the vulcanization time; both processes, after a retardation, go according to the first order law and at the same rate. 4. From the temperature dependence of the rate constants of reciprocal equilibrium swelling, as well as of the increase in stress, an activation energy of 22 kcal/mole can be calculated, in good agreement with the activation energy of dithiocarbamate formation in thiuram vulcanizations.

Studies in the Vulcanization of Rubber. III—Kinetics of Vulcanization of Rubber with Sulfur and Selenium

1930 ◽  
Vol 3 (4) ◽  
pp. 650-659
Author(s):  
John T. Blake
Keyword(s):  
Molecular Weight ◽  
Order Reaction ◽  
Order Equation ◽  
Second Order Reaction ◽  
Experimental Conditions ◽  
Mathematical Basis ◽  
First Order ◽  
Kinetics Of ◽  
Kinetics Of Vulcanization

Abstract A procedure for the determination of combined selenium in rubber has been evolved. The rate of combination of selenium and rubber has been ascertained under certain conditions and shown to follow a first-order equation. A minimum value for the molecular weight of rubber has been estimated. The formation of hard rubber under chosen experimental conditions has been put on a mathematical basis and has been shown to follow a second-order reaction. The soft- and hard-rubber reactions have been shown qualitatively to be successive reactions and the function of accelerators has been discussed. The theory explains the anomalous results obtained by previous investigators.

Vulcanization of Elastomers. 25. Natural Rubber and Synthetic Elastomers with Sulfur and Sulfenamides. I

1960 ◽  
Vol 33 (3) ◽  
pp. 846-856 ◽  
Author(s):  
Walter Scheele ◽  
Horst-Eckart Toussaint ◽  
Yoan-Kun Chai
Keyword(s):  
Reaction Order ◽  
Molar Ratio ◽  
Reactive Intermediate ◽  
Sulfur Concentration ◽  
Kcal Mole ◽  
Experimental Conditions ◽  
Sulfur Vulcanization ◽  
Different Temperatures ◽  
Kinetics Of ◽  
Time Plot

Abstract The sulfur vulcanization of Perbunan N 2818 (acrylonitrile-butadiene) was investigated in the presence of N-cyclohexyl-2-benzothiazolylsulfenamide (CZ) at different temperatures and various concentrations of reactants. The following were found : 1. The decreasing sulfur concentration vs. time plot followed the 0.8th order under all experimental conditions and an activation energy of 28.2 kcal/mole was calculated. 2. When using the cyclohexylammonium salt of MBT as accelerator, sulfur decrease proceeds at the same rate as with CZ. 3. It was concluded from 1 and 2 that even in the presence of CZ, the ammonium salt was the actual accelerator, which forms during the scorch or induction period through reaction of CZ with the rubber. 4. In view of the discrepancy found in the relation of reaction order with respect to time and concentration of reactants, the formation of a reactive intermediate is postulated; the analogy between the kinetics of sulfenamide accelerated sulfur vulcanization, and those accelerated with MBT as well as DPG is pointed out. 5. In connection with 3 the dependence of starting rate as well as rate constant of 0.8th order of the decreasing sulfur concentration on the molar ratio of CZ/S8 and on the sulfur starting concentration is discussed.

Study of the Reaction Kinetics of Aging of Natural Rubber by Infrared Spectrography IV. Influence of Wave Length of Light and Temperature on Light Aging

1955 ◽  
Vol 28 (4) ◽  
pp. 989-998 ◽  
Author(s):  
A. Tkáč ◽  
V. Kellö ◽  
J. Hrivíková
Keyword(s):  
Infrared Spectroscopy ◽  
Natural Rubber ◽  
Linear Relation ◽  
Wave Length ◽  
Side Chain ◽  
Experimental Conditions ◽  
Constant Intensity ◽  
Upper Limit ◽  
Kinetics Of ◽  
Exponential Relation

Abstract The influence of the wave length of radiation on the process of photocatalytic aging of rubber, as well as the relations between the intensity of radiation and the temperature, were studied by infrared spectroscopy. The upper limit of effectiveness of light lies in the range of 4360 A˚. While an increase of temperature greatly accelerates oxidation, an increase of radiation intensity retards it. Numerous analyses reveal an exponential relation between the length of the induction period and the intensity of radiation at constant temperature, and a linear relation between the height of the experimental curves and the temperature at constant intensity. Oxidation destruction and side-chain formation (vulcanization) take place simultaneously during the aging of natural ruber. The relation between these reactions depends on the experimental conditions ; the temperature accelerates oxidation, while the intensity of radiation aids vulcanization.

SERINOL DERIVATIVES FOR THE SUSTAINABLE VULCANIZATION OF DIENE ELASTOMERS

2018 ◽  
Vol 91 (4) ◽  
pp. 701-718 ◽  
Author(s):  
Vincenzina Barbera ◽  
Sara Musto ◽  
Giuseppe Infortuna ◽  
Valeria Cipolletti ◽  
Attilio Citterio ◽  
...  
Keyword(s):  
Natural Rubber ◽  
Building Block ◽  
Induction Time ◽  
High Selectivity ◽  
Rubber Compounds ◽  
Aldehydes And Ketones ◽  
Diene Rubbers ◽  
Kinetics Of ◽  
Derivatives Of ◽  
Kinetics Of Vulcanization

ABSTRACT 2-amino-1,3-propandiol (serinol) was used as the starting building block of synthetic pathways that led to the preparation of innovative chemicals suitable as ingredients for rubber compounds. Serinol based reactions were performed in the frame of a sustainable process, in the absence of any solvent and catalyst, with aldehydes and ketones, such as acetone, cinnamaldehyde and camphor. The synthesis of either imines or oxazolidines was obtained with high selectivity. Serinol, imine and oxazolidine derivatives of serinol were used as accelerator for the vulcanization of diene rubbers. They were proved to be efficient secondary accelerators in silica based compounds based on poly(styrene-co-butadiene) in place of diphenyl guanidine. The kinetics of vulcanization was investigated for natural rubber based compounds in the absence of any filler. With respect to serinol, the imine derivatives were able to enhance the induction time of vulcanization and to afford a similar vulcanization rate.

Studies of the Vulcanization of Rubber. III. Kinetics of Change of Tensile Strength of Natural Rubber during Vulcanization

1954 ◽  
Vol 27 (3) ◽  
pp. 615-621 ◽  
Author(s):  
B. Dogadkin ◽  
B. Karmin ◽  
I. Golberg
Keyword(s):  
Molecular Weight ◽  
Tensile Strength ◽  
Natural Rubber ◽  
Structure Formation ◽  
Linear Function ◽  
General Equation ◽  
Original Material ◽  
Kinetics Of ◽  
Kinetics Of Vulcanization ◽  
Butadiene Styrene

Abstract 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.

Studies on the Kinetics of Vulcanization of Rubber

1964 ◽  
Vol 37 (2) ◽  
pp. 557-562
Author(s):  
H. L. Taneja ◽  
S. Banerjee
Keyword(s):  
Zinc Oxide ◽  
Steady State ◽  
Natural Rubber ◽  
Square Root ◽  
Initiator Concentration ◽  
Appreciable Increase ◽  
Kinetics Of ◽  
Kinetics Of Vulcanization ◽  
Free Sulfur

Abstract The dependence of the rate of accelerated vulcanization of natural rubber (smoked sheet) on the concentration of mercaptobenzothiazole accelerator has been reported on in this paper. The rate of decrease of free sulfur at the steady state has been found to be proportional to the square root of the initiator concentration expressed as grams/100 grams of rubber. The rate has also been found to be enhanced by the addition of 1% of zinc oxide. Higher amounts of zinc oxide does not lead to a further appreciable increase in the rate.

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