Basic Reactions Occurring during Rubber Reclaiming. I. The Influence of Reclaiming Media, Antioxidant, and Defibering Agents on Vulcanized Natural Rubber at 195 Pounds Per Square Inch Gauge Pressure (196.6° C)

1948 ◽  
Vol 21 (4) ◽  
pp. 895-908 ◽  
Author(s):  
D. S. Le Beau
Keyword(s):  
Natural Rubber ◽  
Initial Rate ◽  
Progressive Increase ◽  
Oxidation Products ◽  
Double Bonds ◽  
Open Steam ◽  
Chain Reactions ◽  
Surrounding Atmosphere ◽  
High Initial Rate ◽  
Oxidative Attack

Abstract The influence of surrounding atmosphere, antioxidant, and defibering agents at 196.6° C on the hydrocarbon of rubber was studied by subjecting a laboratory prepared, pure-gum, natural rubber compound to reclaiming in the absence of any reclaiming oils or chemicals. Data obtained on the amount of acetone and chloroform extracts and on the unsaturation of the reclaims and the chloroform extracts could therefore be interpreted in terms of the effect of the factors mentioned above on the rubber hydrocarbon and not as the effect of any chemicals added to the rubber to promote reclaiming. It was found that the effect of the surrounding atmosphere during reclaiming is the predominant factor in the reaction. Acidic surrounding atmospheres result in a slow and rather uniform rate of molecular breakdown and in the formation of small amounts of oxidation products. Apparently no secondary oxidative attack occurs at the double bonds. An open steam atmosphere provides the greatest amount of oxidized products and also a high initial molecular breakdown, followed by a slow progressive increase in it as the reclaiming periods are lengthened. A decrease in the unsaturation value of the acetone extracted reclaim indicates that secondary oxidative attack at the double bonds occurs at long reclaiming intervals. Alkaline reclaiming atmospheres provide little if any oxidation products and result in a very high initial rate of molecular breakdown. Longer reclaiming periods do not change further the amount of molecular breakdown. The very small amounts of oxygen necessary to promote the reclaiming reactions, the dependence of the course of these reactions on the acidity or alkalinity of the surrounding reclaiming media, together with the high initial rate of molecular breakdown reactions under conditions where such rate would be speeded up, permit the tentative explanation of these reactions on the basis of hydroperoxidic chain reactions. Further experiments along this line are being carried out.

Chlorination of Natural Rubber in Solution with Gaseous Chlorine

1953 ◽  
Vol 26 (4) ◽  
pp. 902-911 ◽  
Author(s):  
C. S. Ramakrishnan ◽  
D. Raghunath ◽  
J. B. Pande
Keyword(s):  
Double Bond ◽  
Natural Rubber ◽  
Cyclization Reaction ◽  
Double Bonds ◽  
Chlorine Atoms ◽  
Reaction Stage ◽  
Stage 1 ◽  
Additive Reaction

Abstract The chlorination of rubber solutions by gaseous chlorine was followed by isolating the partially chlorinated products and preparing their ozonides. The ozonides were hydrolyzed, and the acids and aldehydes formed on hydrolysis were determined. By a comparison with the amounts of acids and aldehydes obtained from ozonides of unreacted rubber, the amount of residual isoprenic double bonds present was found. The loss of double bonds attending the introduction of chlorine atoms into the molecule of rubber indicates four definite stages in chlorination : (1) initial substitutive attack by chlorine, with concomitant cyclization, resulting in a loss of one double bond between two isoprenic units, (2) substitution, (3) additive reaction, and (4) essentially substitution. Chlorination of aged rubber solutions differs from the above in that the cyclization reaction (stage 1) seems to be absent.

Longitudinal Cracking in a Carbon Black Filled Natural Rubber Vulcanizate during Chemical Stress Relaxation

1998 ◽  
Vol 71 (2) ◽  
pp. 157-167 ◽  
Author(s):  
G. R. Hamed ◽  
J. Zhao
Keyword(s):  
Stress Relaxation ◽  
Carbon Black ◽  
Natural Rubber ◽  
Longitudinal Crack ◽  
Chemical Stress ◽  
Loading Direction ◽  
Rubber Vulcanizate ◽  
Edge Cracks ◽  
Forced Air ◽  
Oxidative Attack

Abstract Thin specimens of a black-filled, natural rubber vulcanizate have been held in uniaxial tension at 72°C and 200% elongation in a forced air oven. After substantial oxidative attack (inferred from stress relaxation), small edge cracks formed. Initially, these cracks grew perpendicular to the loading direction, but, upon reaching about 0.1 mm in depth, longitudinal crack growth commenced and fracture progressed by a kind of 0°-peel process with “splitting-off” of successive strands of rubber. This phenomenon is attributed to anisotropy in strength caused both by straining and by oxidative attack.

Effect of Sulfur and Dicumyl Peroxide on Vulcanization of Natural Rubber with Tetramethylthiuram Disulfide and Zinc Oxide

1970 ◽  
Vol 43 (6) ◽  
pp. 1294-1310 ◽  
Author(s):  
S. P. Manik ◽  
S. Banerjee
Keyword(s):  
Zinc Oxide ◽  
Stearic Acid ◽  
Natural Rubber ◽  
Reaction Mechanisms ◽  
Elemental Sulfur ◽  
Initial Rate ◽  
Dicumyl Peroxide ◽  
Tetramethylthiuram Disulfide ◽  
Sulfur Vulcanization ◽  
Salient Features

Abstract The salient features of both non-elemental sulfur vulcanization by TMTD and elemental sulfur vulcanization promoted by TMTD both in presence and absence of ZnO and stearic acid have been studied. TMTD increases the rate of DCP decomposition and lowers the crosslinking maxima due to DCP depending on its concentration. However, with higher amounts of TMTD the initial rate of crosslinking is increased with the increased amount of TMTD, while crosslinking maxima are still lowered due to reversion. ZnO or ZnO-stearic acid, however, seems to alter the entire course of the reaction. Both the crosslink formation and TMTD decomposition are much higher in presence of ZnO or ZnO-stearic acid, but stearic acid seems to have no effect. The reaction mechanisms for TMTD accelerated sulfuration in absence and presence of ZnO have also been studied.

Mechanism of Rubber Vulcanization with Sulfur

1938 ◽  
Vol 11 (1) ◽  
pp. 107-130
Author(s):  
W. K. Lewis ◽  
Lombard Squires ◽  
Robert D. Nutting
Keyword(s):  
Natural Rubber ◽  
Temperature Coefficient ◽  
Chemical Reactions ◽  
Chemical Reaction ◽  
Reaction Rate ◽  
Complex Behavior ◽  
Double Bonds ◽  
Irreversible Reaction ◽  
Sulfur Addition

Abstract THAT vulcanization of rubber with sulfur always involves a chemical reaction consisting in the addition of sulfur to the double bonds of the rubber molecule has been conclusively established (18, 28). The facts indicate that this addition of sulfur to rubber is an irreversible reaction (31). The temperature coefficient of the reaction is high, increasing about 2.65 fold per 10° C. at ordinary curing temperatures (31). Furthermore, the reaction is apparently exothermic (4, 24). It is noteworthy that catalysts are apparently necessary, since synthetic rubbers prepared from pure materials add sulfur slowly, if at all. The proteins and perhaps the resins in natural rubber undoubtedly serve as accelerators. The curves for combined sulfur vs. time of cure for typical mixes are shown in Figures 1 and 2. Figure 1 is taken from the data of Kratz and Flower (16); the composition and temperature of cure for this mix are shown in Cranor's Table I (9). Figure 2, curve 1, is from Table I of Eaton and Day (10), and curve 2 from data obtained in this laboratory (27, Table I). Superficial inspection of these curves shows extraordinary divergence of type. Figure 1 is a typical fadeaway curve, characteristic of most chemical reactions, where the reaction rate decreases with decreasing concentration of the reacting materials. Curve 1, Figure 2, is an entirely different type, where the rate of sulfur addition is constant until nearly 70 per cent of the initial sulfur has reacted. Curve 2, Figure 2, shows even more complex behavior. Again the rate is constant in the initial portions of the cure. However, following this period, the rate increases markedly but later falls off, approaching zero, to give an S-shaped eurve.

Statistical Lengths of Rubberlike Hydrocarbon Molecules

1943 ◽  
Vol 16 (3) ◽  
pp. 479-485
Author(s):  
Frederick T. Wall
Keyword(s):  
Natural Rubber ◽  
Physical Properties ◽  
Chemical Properties ◽  
Hydrocarbon Chain ◽  
Point Of View ◽  
Double Bonds ◽  
Gutta Percha ◽  
Cis And Trans ◽  
Trans Structure ◽  
And Chemical Properties

Abstract It has been known for some time that the pure hydrocarbons of balata (or gutta-percha) and natural rubber have the same chemical composition and chemical properties. Both balata and rubber appear to be polymers of isoprene, (C5H8)n, with the same degree of unsaturation. Their physical properties are sufficiently different, however, to make it clear that their structures must differ in some important respect. Since the molecules contain numerous double bonds, it has been suggested that rubber and balata are geometric isomers. Every fourth bond in a rubber or balata molecule is a double bond, so it follows that the possibilities for geometric isomerism are considerable. It was proposed by Meyer and Mark that natural rubber hydrocarbon has a structure for which the molecular chain is cis with respect to all of the double bonds. Balata (or gutta-percha) is then supposed to have a trans-structure throughout, this view having been verified by Fuller and Bunn. It is the purpose of the present paper to consider, from the point of view of recent theories of rubber elasticity, to what extent these structures explain the differences in physical properties. The method to be employed involves calculation of the root mean square lengths of the cis- and trans-structures, which, when compared to their maximum lengths, should give an indication of their extensibilities. In 1932 Eyring treated the problem of the average square length of a hydrocarbon chain. In the present paper a different derivation of Eyring's equation is given (for illustrative purposes), after which this derivation will be extended to the rubberlike molecules with double bonds.

Structural Changes in Vulcanization of Buna-S

1946 ◽  
Vol 19 (3) ◽  
pp. 534-545
Author(s):  
Max H. Keck ◽  
La Verne E. Cheyney
Keyword(s):  
Natural Rubber ◽  
Chemical Reactions ◽  
Structural Changes ◽  
Double Bonds

Abstract In conclusion, the data presented here indicate that two types of chemical reactions take place during the vulcanization of Buna-S stocks of a specific type: (1) a combination with sulfur, which may or may not involve the double bonds in the polymer, and which may be similar in character to the primary vulcanization reaction of natural rubber; (2) a second reaction, presumably polymerization, which accompanies the first and is related to and possibly initiated by it, and which continues on over cure.

Halogenation of Ethylene Propylene Diene Rubbers

1971 ◽  
Vol 44 (4) ◽  
pp. 1025-1042 ◽  
Author(s):  
R. T. Morrissey
Keyword(s):  
Natural Rubber ◽  
Double Bonds ◽  
Optimum Amount ◽  
Ethylene Propylene ◽  
Rubber Compounds ◽  
Rubber Part ◽  
Curing Agents ◽  
Diene Rubbers ◽  
Curing Systems

Abstract The ethylene propylene diene rubbers (EPDM) have been modified by halogenation. The reaction has been considered as one mainly of addition to the double bonds of the diene portion of the rubber. Dehydrohalogenation may occur to varying degrees, depending on the conditions of the reaction and the diene present in the rubber. Part of the halogen is believed to be in the allylic position. The halogenated EPDM may be vulcanized by sulfur as well as many of the curing agents used for other halogen-containing polymers. Both types of curing systems can function in the same compound. Therefore, the halogenated EPDM rubbers can be covulcanized with the highly unsaturated elastomers such as natural rubber, cis polybutadiene, and the SBR rubbers. The excellent properties, resistance to ozone, and flexing, of the halogenated EPDM can be imparted to these elastomers using standard curing systems. Also, the uncured tack of halogenated EPDM can be improved by increasing amounts of natural rubber. In addition, other advantages are adhesion of these blends to other rubber compounds and metal. It has been shown that the cure compatibility properties of the halogenated EPDM can be varied as the halogen is increased in the rubber. Evidence has been presented which shows there is an optimum amount of halogen necessary for the best properties in mixtures with other elastomers.

scholarly journals Mutating the dileucine motif of the human β2-adrenoceptor reduces the high initial rate of receptor phosphorylation by GRK without affecting postendocytic sorting

2010 ◽  
Vol 635 (1-3) ◽  
pp. 9-15 ◽  
Author(s):  
Hibah O. Awwad ◽  
Ellen E. Millman ◽  
Estrella Alpizar-Foster ◽  
Robert H. Moore ◽  
Brian J. Knoll
Keyword(s):  
Initial Rate ◽  
Receptor Phosphorylation ◽  
Dileucine Motif ◽  
High Initial Rate

Mineral Sulfide as Index of Disulfide Cross-Bonding

1947 ◽  
Vol 20 (3) ◽  
pp. 649-663 ◽  
Author(s):  
C. M. Hull ◽  
S. R. Olsen ◽  
Wesley G. France
Keyword(s):  
Natural Rubber ◽  
Cross Linking ◽  
Diallyl Disulfide ◽  
Double Bonds ◽  
Metal Soap ◽  
Sulfide Production ◽  
Sulfur Vulcanization

Abstract 1. The mechanism proposed by Armstrong, Little, and Doak to explain sulfur vulcanization in the presence of metal soap was investigated in polyprene and simpler systems from the viewpoint of the inorganic sulfide produced and, in the case of polyprenes, of the accompanying modulus. 2. Dodecanethiol was found to react with sulfur and zinc soap to produce inorganic sulfide equivalent to the oxidation of 80 to 100 per cent of the thiol to disulfide ; with excess thiol substantially quantitative conversion of sulfur or of zinc soap to inorganic sulfide can be obtained. 3. Several simple olefins were found to react readily with sulfur and zinc soap under vulcanizing conditions. The reaction is promoted by M.B.T. On the basis of the mechanism assumed, the inorganic sulfide formed is sufficient to indicate extensive conversion of the olefin to a substituted diallyl disulfide. 4. Assuming the validity of the proposed mechanism, inorganic sulfide production indicates substantial disulfide cross-linking between α-carbon atoms in conventional cures with natural rubber, and appreciable, though relatively less, cross-bonding of this type in the case of GR-S. The smaller extent of this type of cross-linking with GR-S is believed to result from greater tendency on the part of this elastomer to add the intermediate mercapto compound to double bonds, as proposed in the first paper of this series.

Natural and Synthetic Rubber. I. Products of the Destructive Distillation of Natural Rubber

1929 ◽  
Vol 2 (3) ◽  
pp. 441-451 ◽  
Author(s):  
Thomas Midgley ◽  
Albert L. Henne
Keyword(s):  
Experimental Data ◽  
Natural Rubber ◽  
Atmospheric Pressure ◽  
Experimental Results ◽  
Double Bonds ◽  
Synthetic Rubber ◽  
Single Bonds ◽  
Natural And Synthetic

Abstract Two hundred pounds of pale crepe rubber have been destructively-distilled at atmospheric pressure. The distillate was fractionated and its components identified from C5 to C10, as shown in the table. Assuming that the Staudinger formula is correct, that the single bonds furthest from the double bonds are the weaker spots and that the formation of six-carbon rings is favored, it has been shown that nearly all of the compounds actually isolated could be predicted. The experimental results, together with forthcoming experimental data, are expected to be used to throw light upon the formula of the rubber molecule.

Sign in / Sign up

Export Citation Format

Share Document