Oxidation stability of low-sulfur natural rubber vulcanizates

1966 ◽  
Vol 4 (11) ◽  
pp. 905-912 ◽  
Author(s):  
E. M. Bevilacqua
Keyword(s):  
Natural Rubber ◽  
Oxidation Stability ◽  
Low Sulfur ◽  
Natural Rubber Vulcanizates

Improving oxidation stability and mechanical properties of natural rubber vulcanizates filled with calcium carbonate modified by gallic acid

2010 ◽  
Vol 66 (7) ◽  
pp. 965-977 ◽  
Author(s):  
Sirilux Poompradub ◽  
Thirapat Luthikaviboon ◽  
Srisuwan Linpoo ◽  
Rojrit Rojanathanes ◽  
Pattarapan Prasassarakich
Keyword(s):  
Mechanical Properties ◽  
Calcium Carbonate ◽  
Natural Rubber ◽  
Gallic Acid ◽  
Oxidation Stability ◽  
Natural Rubber Vulcanizates

Investigations in the Field of Rubber Vulcanization. VII. Influence of Organic Accelerators on the Kinetics of Vulcanization and the Properties of Natural-Rubber Vulcanizates

1950 ◽  
Vol 23 (3) ◽  
pp. 563-575
Author(s):  
B. Dogadkin ◽  
B. Karmin ◽  
A. Dobromyslova ◽  
L. Sapozhkova
Keyword(s):  
Activation Energy ◽  
Natural Rubber ◽  
Oxidative Destruction ◽  
Tetramethylthiuram Disulfide ◽  
Vulcanization Kinetics ◽  
Strength Curve ◽  
Increasing Temperature ◽  
Low Sulfur ◽  
Natural Rubber Vulcanizates ◽  
Kinetics Of

Abstract 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 Fraction of Effective Sulfur Crosslinking in High Sulfur-Natural Rubber Vulcanizers

1964 ◽  
Vol 37 (1) ◽  
pp. 225-228
Author(s):  
T. H. Meltzer ◽  
W. J. Dermody ◽  
A. V. Tobolsky
Keyword(s):  
Shear Modulus ◽  
Natural Rubber ◽  
General Pattern ◽  
Amorphous Polymers ◽  
Total Sulfur ◽  
Plateau Modulus ◽  
Low Sulfur ◽  
Natural Rubber Vulcanizates

Abstract Shear modulus measurements as a function of temperature for smoked sheet natural rubber vulcanized with sulfur in amounts between 2 and 34 per cent show the crosslinking efficiency of sulfur to be much lower in natural rubber than in SBR-1000, at least for the particular curing recipe here used. The ratio of crosslinks to total sulfur atoms computed from the rubbery plateau modulus is below 0.07 for all of the natural rubber mixtures. Ratios up to 0.20 were found in SBR mixtures. The shape and slope of the modulus-temperature curves of natural rubber vulcanizates are similar to those of SBR mixtures and are typical of crosslinked amorphous polymers. Consistent displacement of the curves toward higher temperatures and higher rubber modulus as the percentage of sulfur in the recipes is increased also follows the same general pattern found for SBR. Cyclization is concluded to be the primary cause of the low sulfur efficiency in crosslinking both polymers, although polysulfide formation in natural rubber may further reduce the ratio of crosslinks formed per atom of sulfur combined.

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.

High-Resolution Latex-State 13C-NMR Spectroscopy for Natural Rubber Vulcanizates

2007 ◽  
Vol 80 (5) ◽  
pp. 751-761 ◽  
Author(s):  
Seiichi Kawahara ◽  
Jinta Ukawa ◽  
Junichiro Sakai ◽  
Yoshimasa Yamamoto ◽  
Yoshinobu Isono
Keyword(s):  
Nmr Spectroscopy ◽  
High Resolution ◽  
Natural Rubber ◽  
13C Nmr ◽  
Multiple Bond ◽  
Natural Rubber Latex ◽  
13C Nmr Spectroscopy ◽  
Rubber Latex ◽  
Aliphatic Carbon ◽  
Natural Rubber Vulcanizates

Abstract Crosslinking junctions of natural rubber vulcanizates were characterized by high-resolution latex-state 13C-NMR spectroscopy. Vulcanized natural rubber latex was prepared by two methods: i.e., vulcanization of the rubber latex and cryogenic crushing of a rubber sheet vulcanized on a hot press. High-resolution latex-state 13C-NMR spectroscopy was attained even after vulcanization of the rubber latex, as is evident from no background in spectrum and narrow half width of signals independent of vulcanization time. Small signals at 44 ppm and 57 ppm in the aliphatic carbon region were assigned by measurements of both Distortionless Enhancement by Polarization Transfer (DEPT) and Attached Proton Test (APT) to secondary and tertiary carbons of crosslinking points. The assignment was proved by high-resolution solution-state NMR spectroscopy of vulcanized liquid cis-1,4-polyisoprene as a model, in which DEPT, APT, 2-dimensional 1H-1H correlation (H-H COSY), 2-dimensional 1H-13C correlation (H-C COSY) and 2-dimensional heteronuclear multiple bond correlation (HMBC) measurements were applied.

Influence of Crosslink Characteristics Induced by Aromatic-Based Antioxidants on the Swelling and Stress-Strain Behavior of Natural Rubber Vulcanizates

2003 ◽  
Vol 76 (2) ◽  
pp. 334-347 ◽  
Author(s):  
Tarek M. Madkour ◽  
Rasha A. Azzam
Keyword(s):  
Natural Rubber ◽  
Crosslinking Agent ◽  
Oxidative Degradation ◽  
Thermal Oxidative Degradation ◽  
Stress Strain ◽  
Strain Behavior ◽  
Strain Induced Crystallization ◽  
Elastomeric Chains ◽  
Natural Rubber Vulcanizates ◽  
Induced Crystallization

Abstract Stress-strain measurements were performed on dry and swollen natural rubber vulcanizates prepared using both sulfur as the crosslinking agent and aromatic-based bound antioxidants acting as a second crosslinking agent. The aromatic-based antioxidants were synthesized and analyzed spectroscopically in order to relate the final behavior of the vulcanizates to the nature of the crosslink characteristics. The anomalous upturn in the modulus values of these networks in response to the imposed stress was shown to persist in the dry as well as the swollen state. Since the swollen elastomeric chains cannot undergo a strain-induced crystallization, the abnormal upturns in the modulus values in an absence of a filler were explained on the basis of the limited extensibility of the short chains of networks prepared using two different crosslinking agents in line with earlier modeling predictions. Remarkably, the swelling experiments revealed the increase in the crosslink density of the networks in the early stages of the thermal oxidative degradation procedure indicating a post-cure of the chemically bound antioxidants to the elastomeric chains, which incidentally corresponds to a maximum in the modulus values of the networks. The rheological and other mechanical properties such as the hardness were shown not to have been affected as a result of the incorporation of the chemically bound antioxidants.

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