Structural Changes in Vulcanization of Buna-S

1946 ◽  
Vol 19 (3) ◽  
pp. 534-545
Author(s):  
Max H. Keck ◽  
La Verne E. Cheyney

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.

1938 ◽  
Vol 11 (1) ◽  
pp. 107-130
Author(s):  
W. K. Lewis ◽  
Lombard Squires ◽  
Robert D. Nutting

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.


2008 ◽  
Vol 21 (2) ◽  
pp. 211-214
Author(s):  
Nataliya Sybirna ◽  
Tetyana Buslyk ◽  
Nataliya Klymyshyn ◽  
Andriy Hnatush ◽  
Maria Duk ◽  
...  

2016 ◽  
Vol 49 (5) ◽  
pp. 381-396 ◽  
Author(s):  
Farzad A Nobari Azar ◽  
Murat Şen

Natural rubber/chloroprene rubber (NR/CR) blends are among the commonly used rubber blends in industry and continuously are exposed to severe weather changes. To investigate the effects of accelerator type on the network structure and stress relaxation of unaged and aged NR/CE vulcanizates, tetramethyl thiuram disulfide, 2-mercaptobenzothiazole, and diphenyl guanidine accelerators have been chosen to represent fast, moderate, and slow accelerator groups, respectively. Three batches have been prepared with exactly the same components and mixing conditions differing only in accelerator type. Temperatures scanning stress relaxation and pulse nuclear magnetic resonance techniques have been used to reveal the structural changes of differently accelerated rubber blends before and after weathering. Nonoxidative thermal decomposition analyses have been carried out using a thermogravimetric analyzer. Results indicate that there is a strong interdependence between accelerator type and stress relaxation behavior, network structure, cross-linking density, and aging behavior of the blends. Accelerator type also affects decomposition energy of the blends.


1953 ◽  
Vol 26 (4) ◽  
pp. 902-911 ◽  
Author(s):  
C. S. Ramakrishnan ◽  
D. Raghunath ◽  
J. B. Pande

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.


2014 ◽  
Vol 79 (12) ◽  
pp. 1491-1503
Author(s):  
Vesna Jovanovic ◽  
Jelena Acimovic ◽  
Vesna Dimitrijevic-Sreckovic ◽  
Ljuba Mandic

It has been verified that serum N-acetyl-?-D-glucosaminidase (NAG) activity is elevated in diabetes, but there are no reports about changes of the sialic acid (SA) content in the carbohydrate parts of NAG A form and its influence on total NAG activity changes in type 1 diabetes mellitus patients without and with secondary complications. NAG A forms were isolated, purified and characterized from the serum of 81 IDDM patients with and without secondary complications (retinopathy, polyneuropathy and nephropathy) and 25 healthy persons. The content of ?-2,6-bound SA and isoenzyme patterns of purified A form, total NAG and A form activities were determined. In all diabetic groups, A form sialylation levels were 2-3.5 times lower compared to control, while their acidities (fractions with pI 4.25-5.1) increased, particularly with progression of secondary complications. Total serum NAG activities and percentages of A form were significantly higher (P<0.001) in all diabetic groups and negatively correlated with the ?-2,6-bound SA content of the A form. In addition, they decreased as secondary diabetic complications became more complex. Observed changes could be the consequence of structural changes in the A form due to significant increase in its acidity, i.e. negative charge which originate from groups other than SA.


2004 ◽  
Vol 5 (1) ◽  
pp. 65-77 ◽  
Author(s):  
Anders A. F. Sima ◽  
Weixian Zhang ◽  
George Grunberger

The most common microvascular diabetic complication, diabetic peripheral polyneuropathy (DPN), affects type 1 diabetic patients more often and more severely. In recent decades, it has become increasingly clear that perpetuating pathogenetic mechanisms, molecular, functional, and structural changes and ultimately the clinical expression of DPN differ between the two major types of diabetes. Impaired insulin/C-peptide action has emerged as a crucial factor to account for the disproportionate burden affecting type 1 patients. C-peptide was long believed to be biologically inactive. However, it has now been shown to have a number of insulin-like glucoseindependent effects. Preclinical studies have demonstrated dose-dependent effects onNa+,K+-ATPase activity, endothelial nitric oxide synthase (eNOS), and endoneurial blood flow. Furthermore, it has regulatory effects on neurotrophic factors and molecules pivotal to the integrity of the nodal and paranodal apparatus and modulatory effects on apoptotic phenomena affecting the diabetic nervous system. In animal studies, C-peptide improves nerve conduction abnormalities, prevents nodal degenerative changes, characteristic of type 1 DPN, promotes nerve fiber regeneration, and prevents apoptosis of central and peripheral nerve cell constituents. Limited clinical trials have confirmed the beneficial effects of C-peptide on autonomic and somatic nerve function in patients with type 1 DPN. Therefore, evidence accumulates that replacement of C-peptide in type 1 diabetes prevents and even improves DPN. Large-scale food and drug administration (FDA)-approved clinical trials are necessary to make this natural substance available to the globally increasing type 1 diabetic population.


1964 ◽  
Vol 37 (2) ◽  
pp. 563-570 ◽  
Author(s):  
Bryan Ellis ◽  
G. N. Welding

Abstract A procedure is described for estimating indirectly the contribution of vulcanization reactions to the build-up of network structure. This method is useful with technically important vulcanizing systems for which no direct method of estimation has been found. Errors of the theory of high elasticity are avoided by using published results, such as those of Moore and Watson of direct chemical estimates obtained with a special vulcanizing system that is chemically well understood. Reliance on the theories of end correction and swelling is also avoided by using published experimental relations. The method is applicable to any linear primary polymer of arbitrary molecular weight and any suitable swelling liquid, for which the required reference data have been obtained.


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