The Mechanism of the Deactivating Effect

1957 ◽  
Vol 30 (4) ◽  
pp. 1166-1167
Author(s):  
Jeanle Bras ◽  
Jean Claude Danjard
Keyword(s):  
Test Piece ◽  
Chemical Structure ◽  
Relaxation Method ◽  
Chain Scission ◽  
Initial Structure ◽  
Vulcanized Rubber ◽  
Rubber Compounds ◽  
Relaxation Measurements ◽  
Aging Properties ◽  
Continuous Relaxation

Abstract It was shown by one of us that certain substances, called deactivates, can protect vulcanized rubber against aging by a process which is different from that of antioxidants. The proposed mechanism involved a deactivation of the primary peroxides by transforming them into oxides of rubber without causing any chain scission. This hypothesis, however, did not appear to be completely satisfactory. In fact, deactivators do not protect raw rubber against oxidation, but actually accelerate its degradation in solution, especially in the presence of a peroxide which enhances this deterioration. Moreover, if was shown that the deactivators possess a chemical structure which is very similar to that of certain vulcanization accelerators, and also that they have an effect on the vulcanization. This had led to the suggestion that their effect could be attributed to the initial structure of the vulcanized rubber. We have considered the possibility of obtaining some useful information on this subject by means of stress relaxation measurements which involve the decrease in tensile strength with time of a stretched test piece. The measurements were carried out either by maintaining the test piece at constant elongation (continuous relaxation), or by stretching the relaxed sample to a constant elongation from time to time (discontinuous relaxation). It has been established that the continuous relaxation method accounts solely for the chain scissions which are produced in the vulcanized rubber network, whereas the intermolecular linkages formed during the tests contribute to the discontinuous relaxation picture. The results of some preliminary experiments we have carried out are given in Figure 1. Two rubber compounds, accelerated with diphenylguanidine and mercaptobenzothiazole, respectively, and known to have quite different aging properties, were employed. Vulcanizates containing either an antioxidant A (phenyl-2-naphthylamine) or a deactivator D (zinc mercaptobenzimidazolate) were compared with the control vulcanizates T.

A Study of the Mechanism of the Deactivation Effect

1954 ◽  
Vol 27 (1) ◽  
pp. 157-164 ◽  
Author(s):  
Jacques Le Foll
Keyword(s):  
Chemical Structure ◽  
A Priori ◽  
Natural Aging ◽  
Chain Scission ◽  
Nitro Compounds ◽  
Active Part ◽  
Relaxation Phenomena ◽  
Chain Molecules ◽  
Vulcanized Rubber ◽  
The Subject

Abstract The only method by which significant differences between the effects of antioxygenic agents and deactivating agents can be detected has been found to be a study of relaxation phenomena. An investigation by this method has also furnished further support to the theories of Tobolsky and his coworkers. The changes which take place during aging in the physical properties of vulcanized rubber are the result of two independent phenomena which occur simultaneously: (1) chain scission, and (2) formation of intermolecular bonds. As far as the aging of vulcanizates of natural rubber under normal conditions, e.g., socalled natural aging, is concerned, the chief phenomenon involved is scission of the chain molecules. In principle, therefore, there are two methods for combatting the deterioration of rubber on aging: (1) to impede chain scission by obstructing the fixation of oxygen, and (2) to promote the progressive formation of intermolecular bonds which compensate for the effects of the scission process. The first of these processes is that in which antioxygenic agents play the active part; in the second process, deactivating agents play the active part. From this viewpoint, deactivating agents play a part analogous to that of accelerators, and they may be regarded as representing a special type of acceleration. This theory makes possible a better understanding of a number of facts which, a priori, seem surprising: (1) the relationships of both chemical structure and mode of action of accelerators and deactivating agents, and (2) the protective effect of litharge, peroxides, and nitro compounds, all of which are vulcanizing agents. With respect to the intimate mechanism of the deactivating effect, one question remains unanswered, viz., how are intermolecular bonds formed under the influence of deactivating agents? This question recalls the question of the function of vulcanization accelerators, which has been the subject of many investigations, but which still remains a mystery.

COMPARISON BETWEEN RICE HUSK SILICA-FILLED EPOXIDIZED NR CROSS-LINKED WITH FUMARIC ACID AND VULCANIZED WITH SULFUR

2018 ◽  
Vol 92 (2) ◽  
pp. 286-297
Author(s):  
Rohani Abu Bakar ◽  
Rosiyah Yahya ◽  
Seng Neon Gan
Keyword(s):  
Tensile Strength ◽  
Rice Husk ◽  
Fumaric Acid ◽  
Precipitated Silica ◽  
Vulcanized Rubber ◽  
Dilute Sulfuric Acid ◽  
Rubber Compounds ◽  
Aging Properties ◽  
The Cost ◽  
Stiffening Effect

ABSTRACT A wide variety of fillers are used in the rubber industry to modify the properties of rubber compounds and reduce the cost of products in different applications. Silica produced from rice husk could be an alternative filler to commercial precipitated silica widely used in sulfur-vulcanized rubber formulations. High purity amorphous silica (>99% SiO2) was produced after pretreatment of rice husk with dilute sulfuric acid before combustion at 600 °C. Epoxidized NR (ENR) with 50 mol% epoxide groups (ENR50) containing various silica loadings was cured with fumaric acid via reactions of the epoxide group with –COOH, whereas sulfur vulcanization used the carbon–carbon double bonds, as confirmed by Fourier transform infrared spectroscopy (FTIR) analysis. Increasing silica loading in both of types of samples led to an increase in rheometer torque and a decrease in percentage of solvent swelling due to the stiffening effect of silica, with no change in glass-transition temperature, which presumably was due to no chemical reaction between silica and ENR. The tensile strength of fumaric acid–cured ENR50 slightly increased with increasing silica loading and remained unchanged upon aging. The sulfur-vulcanized ENR50 containing 30 phr silica exhibited higher tensile strength, but further increase of silica weakened these properties. After aging, the tensile strength reduced by 5–7 MPa. Fumaric acid–cured rubbers have shown superior aging properties.

Aging of Natural Rubber Vulcanizates in the Presence of Dithiocarbamates

1959 ◽  
Vol 32 (3) ◽  
pp. 739-747 ◽  
Author(s):  
J. R. Dunn ◽  
J. Scanlan
Keyword(s):  
Stress Relaxation ◽  
Natural Rubber ◽  
Protective Action ◽  
Dicumyl Peroxide ◽  
Vulcanized Rubber ◽  
Aging Properties ◽  
Photochemical Aging ◽  
Natural Rubber Vulcanizates

Abstract The thermal and photochemical aging of extracted dicumyl peroxide-, TMTD (sulfurless)- and santocure-vulcanized rubber, in presence of a number of metal and alkylammonium dithiocarbamates, has been investigated by measurements of stress relaxation. The dithiocarbamates have a considerable protective action upon the degradation of peroxide- and TMTD-vulcanizates, but they accelerate stress decay in santocure-accelerated vulcanizates. The reasons for this behavior are discussed. It is suggested that the excellent aging properties of unextracted TMTD vulcanizates are due to the presence of zinc dimethyldithiocarbamate formed during vulcanization.

The Chemical Structure Responsible for the Deactivating Effect of Compounds Which Protect Rubber from Deterioration by Oxygen

1951 ◽  
Vol 24 (3) ◽  
pp. 638-639
Author(s):  
Jean Le Bras ◽  
Jacques Le Foll
Keyword(s):  
Nitrogen Atom ◽  
Systematic Study ◽  
Chemical Structure ◽  
Thiol Group ◽  
Vulcanized Rubber ◽  
Thiol Form

Abstract One of the present authors has already offered evidence which indicates the existence of a deactivating effect, whereby vulcanized rubber is protected against deterioration by oxygen. This effect is evident with such compounds as mercaptobenzimidazole (I), mercaptobenzoxazole, and ethylene-bis (N,N′-phenylthiourea) (II), and the phenomenon seems to be connected in some way with the presence in the molecule of a thiol group united to a nitrogen atom under such conditions that the possible tautomerism between the thion and thiol forms (III) is probably displaced toward the thiol form. We have completed these earlier experiments by a more systematic study, which has included an examination of the influence of cyclization, the nature of the ring, and hetero atoms.

Effect on Vulcanized Rubber Compounds of Immersion in Boiling Water

1931 ◽  
Vol 4 (3) ◽  
pp. 426-436
Author(s):  
K. J. Soule
Keyword(s):  
Water Absorption ◽  
Room Temperature ◽  
Anomalous Behavior ◽  
Boiling Water ◽  
Vulcanized Rubber ◽  
Rubber Compounds ◽  
Different Temperatures ◽  
Actual Change

Abstract Further work is very desirable on the effect of different accelerators, antioxidants, and fluxes. It is possible that their study will throw more light on the mechanism of the swelling phenomena, and also help to explain the anomalous behavior of some of the fillers tested. It would also seem to be worth while to study the action of a few selected stocks in water, at several temperatures between room temperature and 100° C., to determine if the water absorption and swelling merely increase with rising temperatures, or whether there might be an actual change in behavior at different temperatures.

Chemical Structure of Vulcanized Rubber

1939 ◽  
Vol 12 (1) ◽  
pp. 43-55
Author(s):  
J. R. Brown ◽  
E. A. Hauser
Keyword(s):  
Chemical Structure ◽  
Empirical Knowledge ◽  
Extensive Investigation ◽  
Practical Application ◽  
True Nature ◽  
Rubber Industry ◽  
Vulcanized Rubber ◽  
Metallic Salts ◽  
Other Substances

Abstract A CENTURY ago, Charles Goodyear in America and Th. Hancock in England found that the properties of crude rubber could be greatly improved by heating it with sulfur. The product resulting was more elastic, more resistant to tear and abrasion, less affected by solvents, and decidedly less thermoplastic. The treatment of rubber to give these desired properties is known generally as vulcanization and must be considered as the basis for the enormous growth of the rubber industry and the extensive use of rubber products in our everyday life. Broadly speaking, vulcanization involves the reaction, in some fashion, of sulfur with rubber. Extensive investigation has revealed other substances, such as benzoyl peroxide or polynitrobenzenes, which can transform rubber into a “vulcanized” condition. Experience has also shown that metallic salts of zinc or lead and especially certain organic compounds called “accelerators” greatly affect the rate of vulcanization, and these are favorably employed in practice. A vast amount of empirical knowledge has been gained which has greatly improved the practical application of vulcanization and the quality of rubber products, but which has failed as yet to reveal a complete picture of the true nature of the process.

Studies in the Vulcanization of Rubber. IV—A Theory of Vulcanization of Rubber

1930 ◽  
Vol 3 (4) ◽  
pp. 659-667
Author(s):  
G. R. Boggs ◽  
J. T. Blake
Keyword(s):  
Electrical Properties ◽  
Joule Effect ◽  
Vulcanized Rubber ◽  
Chemical Theory ◽  
Rubber Compounds ◽  
Kinetics Of ◽  
Kinetics Of Vulcanization

Abstract A new theory has been advanced which, it is believed, explains completely the various phenomena connected with the vulcanization of rubber. It is entirely a chemical theory based on the existence of two separate and distinct rubber compounds, soft vulcanized rubber and ebonite. The theory explains satisfactorily the aging of rubber, the variation in combined sulfur at optimum cure caused by acceleration, the kinetics of vulcanization, the characteristics of various vulcanizing agents, the thermochemistry of vulcanization, the electrical properties of rubber, the reclaiming of rubber, and the Joule effect. A brief review and discussion of the phenomena and past theories of vulcanization have also been given.

Crystallization of Vulcanized Rubber

1941 ◽  
Vol 14 (2) ◽  
pp. 347-355 ◽  
Author(s):  
Norman Bekkedahl ◽  
Lawrence A. Wood
Keyword(s):  
Practical Importance ◽  
X Ray Diffraction ◽  
X Ray ◽  
Vulcanized Rubber ◽  
Rubber Compounds ◽  
Single Exception ◽  
Quantitative Results ◽  
The Subject ◽  
Low Sulfur Content ◽  
Low Sulfur

Abstract The formation of crystals at room temperature by stretching rubber, vulcanized or unvulcanized, has been the subject of considerable study. The crystallization of unstretched rubber at low temperatures is also well known, but with a single exception to be discussed later, the effect has commonly been considered to be limited to the unvulcanized material. In the present investigation, however, the crystallization of unstretched specimens of vulcanized rubber of low sulfur content has been accomplished. In commercial vulcanized rubber products, crystallization has not hitherto been recognized as a factor of practical importance. It is probably significant in cold climates, where some rubber products slowly undergo a great increase in rigidity and permanent set. Automobile traffic counters, for example, have been rendered inoperative by the hardening of the rubber tubing used with them. Laboratory tubing and other products made of a number of different commercial rubber compounds have become rigid after storage for some weeks in a refrigerator at about 0° C. Previous work on unvulcanized rubber showed that it can be crystallized at temperatures between + 10° and −40° C, the crystals melting in a range from about 6° to 16° C. Crystallization and fusion are accompanied by changes in volume, heat capacity, light absorption, birefringence, x-ray diffraction, and mechanical properties such as hardness. x-Ray diffraction and birefringence, of course, give the most direct evidence of crystalline structure, but in the present work change of volume, measured in a mercury-filled dilatometer, was chosen as the criterion of crystallization or fusion. Quantitative results are more easily obtained in this manner, and the experimental observations are simple. Furthermore, the method is well adapted to continuous observations over long periods of time, such as were found necessary in the present work.

Molecular Structure and Macroscopic Properties of Synthetic Cis-Poly(Isoprene)

1974 ◽  
Vol 47 (2) ◽  
pp. 342-356 ◽  
Author(s):  
V. A. Grechanovskii ◽  
I. Ya Poddubnyi ◽  
L. S. Ivanova
Keyword(s):  
Molecular Weight ◽  
Functional Groups ◽  
Chemical Structure ◽  
Sol Gel ◽  
Average Molecular Weight ◽  
Dense Network ◽  
Green Strength ◽  
Gel Fraction ◽  
Rubber Compounds ◽  
Processing Properties

Abstract By changing the sol-gel ratio and the structure of the gel fraction it is possible to obtain various grades of synthetic cis-poly(isoprene) which show promise for different applications in the tire and mechanical rubber goods industries. The processability of commercial SKI-3 rubber (at a given average molecular weight of sol) depends mainly on the structure of the gel fraction. Thus, for example, inferior processing properties of rubber compounds is associated primarily with the presence of tight gel. The content and structure of the gel fraction also significantly affect plasto-elastic properties of raw rubbers, e.g. a low plasticity of raw rubbers owes to the increased content of gel fraction. The reduced green strength of compounds based on SKI—3 rubber is accounted for by its chemical structure. Conventional methods used to change the properties of rubbers (including the variation in molecular weight, molecular weight distribution, branching degree, and variation in the content and structure of gel fraction) cannot be considered to be adequate to tackle the problem of the green strength of SKI—3 black stocks. The way to solve the problem appears to be the introduction of functional groups into the polymer chain at the stage of synthesis or processing. These functional groups should be active as to the formation of labile rubber—carbon black—rubber and/or rubber—rubber bonds. High purity of microstructure is necessary but not sufficient for obtaining the required level of green strength of compounded SKI—3. The gel fractions of SKI—3 rubber yield vulcanizates with a more dense network than the corresponding sol vulcanizates. The temperature dependence of the tensile strength is controlled by the network density of vulcanizates from high cis-1,4 poly(isoprene).

Sign in / Sign up

Export Citation Format

Share Document