Mechanochemical Phenomena in Polymers. III. Strength of the Bond between Elements of Multiply Polymer Articles

1960 ◽  
Vol 33 (4) ◽  
pp. 953-958
Author(s):  
G. L. Slonimskiĭ ◽  
G. P. Drugova

Abstract 1. The basis of the process of ply separation of multiply rubber articles under repeated deformations is fatigue of the material in the region of the joint of the plies, which is a mechanochemical process, as previously studied, consisting of the development of chain chemical processes initiated by free radicals which are formed in the mechanical scission of chemical bonds in the molecules. 2. By the addition of substances inhibiting chain radical processes to the polymer it is possible to raise considerably the strength of the bond between elements of multiply vulcanized rubber articles.

1963 ◽  
Vol 36 (2) ◽  
pp. 480-487
Author(s):  
E. V. Reztsova ◽  
B. T. Kipkina ◽  
G. L. Slonimskii

Abstract 1. The substantial effect of inhibitors and initiators of chain radical processes on the change in the properties of rubbers in milling, as well as on the resistance of vulcanizates to fatigue, has been shown. This indicates a mechanochemical mechanism for processing of polymers and in the fatigue of elastomers. The act of mechanical scission of chemical bonds, with the formation of free radicals which initiate the secondary chain processes, rests on these processes. 2. The possibility has been shown of regulating the properties of polymers during processing, and also of increasing the dynamic fatigue resistance of vulcanizates by incorporating small quantities of additives active in regard to free radicals.


1960 ◽  
Vol 33 (4) ◽  
pp. 946-952
Author(s):  
E. V. Reztsova ◽  
B. G. Lipkina ◽  
G. L. Slonimskiĭ

Abstract 1. The substantial effect of inhibitors and initiators of chain radical processes on the change in the properties of rubbers in milling, as well as on the resistance of vulcanizates to fatigue, has been shown. This indicates a mechanochemical mechanism of the processes occurring in processing polymers and of the fatigue of highly elastic materials (e.g., rubber vulcanizates). The act of mechanical scission of chemical bonds, with the formation of free radicals which initiate the secondary chain processes, rests on these processes. 2. The possibility has been shown of regulating the properties of polymers in the course of their industrial processing, and also of increasing the dynamic fatigue resistance of vulcanizates by incorporating small quantities of additives active in regard to free radicals.


1953 ◽  
Vol 26 (4) ◽  
pp. 759-763 ◽  
Author(s):  
B. Dogadkin ◽  
Z. Tarasova

Abstract According to the hypotheses developed by the authors, vulcanized rubber is a system in which the molecular chains are united by local molecular and chemical bonds of varying intensity. The concentration, distribution, and strength of these bonds determine the principal physical and mechanical properties of the vulcanizates. Consequently the study of the structure of the vulcanizate is of primary practical value. The explanation of the nature of the bonds in a vulcanizate by chemical methods is very difficult, mainly because of the impossibility of distinguishing the specific chemical groups which enter into the composition of the different molecular chains from those bonds between the chains which are responsible for the development of spatial structures. From this view point, the thermo-mechanical method described below, which is based on the study of stress relaxation at different temperatures, is of great significance. As was shown by Dogadkin and Reznikovskii˘, the delayed stress relaxation in a vulcanizate at temperatures up to 70° C is caused by rupture of the local intermolecular bonds and the regrouping of the structural elements of the polymeric chains without destruction of the chemical bonds between them. Accordingly, after some time at these temperatures, a practically balanced stress is established, which depends on the number of the stronger bonds remaining. At temperatures above 70° C, rupture of the chemical bonds between the chains takes place; its speed increases with decrease of the energy activating the rupture of the given type of bond. Particularly in the case of sulfur vulcanizates, we can assume that the following types of bonds exist between the chains of the rubber: (1) —C—C—, which develop as a result of the polymerizationprocesses; (2) —C—S—C— monosulfide; (3) —C—S—S—C— disulfide, and (4) —C—Sn—C— polysulfide, formed as a result of the direct participation of the vulcanizing agent, sulfur, in the process of joining of the molecular chains. The energy of these chains can be estimated as 62.7 kcal, per mole for C—C, 54.5 kcal. per mole for C—S, and 27.5 kcal. per mole for the —S—S bond. Naturally, the heat stability of a vulcanizate will depend on which of the indicated types of bonds predominates.


1962 ◽  
Vol 35 (5) ◽  
pp. 1308-1341 ◽  
Author(s):  
Jean LeBras

Abstract According to the partial conclusions drawn from the results given in each of the three chapters of this review, one can say that the question of reinforcement by resins, if it has not yet attained the aims sought for, has accumulated a great deal of useful information and now seems in a position to make rapid progress. The most significant point that seems to emerge is the necessity for the establishment of strong chemical bonds between the resin particle and the elastomer. This is undoubtedly not sufficient, and other characteristics of the particle must also intervene; but we have said above that one could now imagine a systematic study of the influence of these characteristics, and we need not return to it here. Many questions are still posed and the investigator will have the task of answering them. We consider it important to insist, however, in this conclusion, on some very recent results which it seemed preferable to us to mention here rather than to incorporate them in the text. In fact, they will either bring a confirmation on the influence of chemical bonds or show the possibility of preparing rubbers which should lend themselves remarkably well to this kind of reinforcement. In studying the crosslinking phenomena that involve the well known hardening of dry natural rubber on storage, Sekhar has shown that reactive groups are present as in integral part of the polyisoprene chain when it leaves the tree. These reactive groups have the characteristic property of carbonyl groups or, more specifically, aldehyde groups. They are responsible for crosslinking of the rubber molecules, and reactive monofunctional amines or other carbonyl reagents are capable of inhibiting this crosslinking effectively. From the critical concentration of reagent required to inhibit hardening, one has to postulate the presence of 9 to 29 aldehyde groups per polyisoprene molecule, assuming a molecular weight of 1,000,000). Because of the presence of these aldehyde groups on the chain of the rubber hydrocarbon, one was led logically to suppose that molecules of aminoplast resins formed in the latex might be fixed chemically on the rubber through the aid of these groups. This is what Sekhar and Angove realized with hydrazine-formalde-hyde resins. At a concentration of 5% and less of resin based on rubber, the latex remained fluid with no tendency to gel. Films and foam rubbers prepared from such resin latex showed considerable reinforcement: thus for a 3% resin content, for example, the tensile strength of a latex film passes from 285 kg/cm2 for the control to 362 kg/cm2 (the elongation in both cases being 925%), the 600% modulus from 32 to 75 kg/cm2, the tear resistance from 64 to 100 kg/cm. It is therefore with the greatest interest that one should consider such reinforcement results obtained with such a small proportion of resin; they emphasize the very important part that must be played by a strong chemical bond between the filler particle and the elastomer. It is evident, however, that the small proportion of aldehyde groups present on the rubber molecule limits the possibilities of such a fixation and must not permit to obtain the maximal reinforcing effects. That is why it seems necessary to pay a great attention to the reaction of glyoxal on rubber, which is endowing this latter with aldehyde-α alcohol side groups and gives it the reactivity toward the resins that seems to be desirable. We may therefore think that the years to come will bring into this field new and useful results, with a view toward the improvement of the characteristics of vulcanized rubber and ever-widening development of its application.


1963 ◽  
Vol 36 (2) ◽  
pp. 473-479
Author(s):  
G. L. Slonimskii ◽  
E. V. Reztsova

Abstract 1. The authors demonstrate the essential role of mechanochemical phenomena in processing. Attention is paid to the necessity of taking into account the phenomenon of chemical flow. 2. From the example of various vulcanizates there is demonstrated the possibility of mechanical processing of crosslinked polymers. Attention is paid to the significance of mechanochemical phenomena in reclaiming. 3. A demonstration is given of the influence of small additions of substances which form free radicals or which interact with them, upon the kinetics of the alteration of the properties of a polymer on prolonged milling. Attention is paid to the possibility of controlling the properties of a polymer during processing. 4. The authors show the necessity of taking into account the phenomenon of chemical flow in developing objective methods of laboratory assessment of the technological properties of polymers.


1959 ◽  
Vol 32 (1) ◽  
pp. 231-243 ◽  
Author(s):  
E. I. Tinyakova ◽  
B. A. Dolgoplosk ◽  
V. N. Reĭkh

Abstract 1. The mechanism of action of various oxidation-reduction systems containing organic reducing agents, iron salts, and oxygen, is investigated, and it is shown that in hydrocarbon media these systems are an effective source of free radicals at low temperatures. 2. The possibility of utilization of these systems for initiation of a chain process of oxidative degradation of unsaturated and some saturated polymers, at low temperatures, is shown.


2012 ◽  
Vol 560-561 ◽  
pp. 395-400
Author(s):  
Alexander Scheeline ◽  
Woo Hyuck Choi ◽  
Edward T. Chainani ◽  
Khan T. Ngo

Ultrasonically-levitated drops have been widely studied for materials processing and for sample preparation for chemical analysis. We report on the development of such drops for study of kinetics of enzyme-catalyzed reactions and other chemical processes. We review how to simply and reliably levitate drops, discuss why such drops are desirable for studying biochemical reactions, especially those generating or consuming free radicals, and report progress towards routine kinetics measurements in microliter drops.


2001 ◽  
Vol 12 (4) ◽  
pp. 273-298 ◽  
Author(s):  
Irina A Buhimschi ◽  
Carl P Weiner

Oxygen radicals and reactive oxygen species are normal attributes of aerobic life. In most molecules, the electrons are paired and, with the exception of hydrogen, the four outer most pairs of each atom form chemical bonds. Electrons are in a relatively stable energy state when paired. A free radical is a molecule with an unpaired electron. Free radicals of oxygen are of particular importance to living organisms in which they are involved in the genesis of a wide array of diseases and physiological processes (e.g. life span and ageing).


Synthesis ◽  
2019 ◽  
Vol 51 (24) ◽  
pp. 4531-4548 ◽  
Author(s):  
Tong Zhang ◽  
Yue-Hua Wu ◽  
Nai-Xing Wang ◽  
Yalan Xing

C(sp3)–H Bonds are the most common structures in organic molecules. In recent years, the direct functionalization of C(sp3)–H bonds has attracted wide attention and made significant progress. This review mainly focuses on C(sp3)–H bond functionalization of alkanes with or without functional groups via radical processes reported since 2017. In particular, three methods of generating free radicals are discussed: the use of a radical initiator such as TBHP or DTBP; photocatalysis, and via 1,5-hydrogen atom transfer (1,5-HAT).1 Introduction2 C(sp3)–H Bond Functionalization of Alkanes3 C(sp3)–H Bond Functionalization of Alkanes with a Functional Group4 Conclusions


1959 ◽  
Vol 32 (1) ◽  
pp. 244-256
Author(s):  
B. A. Dolgoplosk ◽  
E. I. Tinyakova

Abstract The following redox systems capable of initiating radical polymerizations are discussed: (1) Systems of the first type, where the reaction leads to the formation of a single radical: (a) Mechanism of action of reversible systems involving dienols and salts of metals of variable valency. (b) Mechanism of the decomposition of hydroperoxides by the action of salts of metals of variable valency in their higher oxidation states. (2) Systems of the second type, where the reaction leads to the formation of two radicals. Mechanism of action and effectiveness of systems involving hydroperoxides, quinol, and sulfite. (3) Systems of the third type, in which the formation of free radicals is not directly linked to the redox process. Mechanism of action of systems involving diazoamino compounds and “polyamine” systems. (4) Crosslinking of unsaturated polymers at low temperatures by the action of redox systems. Transition from crosslinking to destructive processes in presence of oxygen.


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