Vulcanization Reactions in Butyl Rubber. Action of Dinitroso, Dioxime, and Related Compounds

1946 ◽  
Vol 19 (4) ◽  
pp. 900-914 ◽  
Author(s):  
John Rehner ◽  
Paul J. Flory
Keyword(s):  
Natural Rubber ◽  
Chemical Reactions ◽  
Active Agent ◽  
Butyl Rubber ◽  
Nitroso Compounds ◽  
Cross Linking ◽  
Oxidizing Agent ◽  
Nitroso Group ◽  
Oxidizing Agents ◽  
Related Compounds

Abstract Experiments have been carried out to determine the chemical reactions that occur when Butyl rubber is vulcanized by quinone dioxime or related compounds. Observations have been made of the reactions of these substances with simple olefins, and of the effect of oxidizing agents on the dioxime-type of vulcanization of Butyl in solution. The theory is proposed that, in the vulcanization of Butyl by quinone dioxime or its esters, in presence of oxidizing agents, the active agent is p-dinitrosobenzene formed by oxidation of the dioxime. Chemical reactions are suggested for the subsequent cross-linking or vulcanizing steps, and the results of confirmatory experiments are presented. p-Dinitrosobenzene and other polynitroso compounds are active vulcanizing agents for Butyl, natural rubber, Buna-S, Buna-N, and Neoprene, and do not require the addition of an oxidizing agent. It is suggested that vulcanization of natural rubber by polynitro compounds involves their reduction to corresponding nitroso compounds as the first step, and that the nitroso group adds to rubber to produce cross-linkages.

Heats of Vulcanization of Synthetic Rubbers

1944 ◽  
Vol 17 (2) ◽  
pp. 404-411 ◽  
Author(s):  
P. L. Bruce ◽  
R. Lyle ◽  
J. T. Blake
Keyword(s):  
Carbon Black ◽  
Natural Rubber ◽  
Chemical Reactions ◽  
Side Reaction ◽  
Heat Evolution ◽  
Butyl Rubber ◽  
Vulcanized Rubber ◽  
Principal Reaction ◽  
Low Sulfur ◽  
Quantity Of Heat

Abstract 1. The heats of vulcanization for natural rubber and Buna-S are nearly equal. The data for both materials indicate two different chemical reactions during vulcanization. At low sulfur percentages, the principal reaction forms soft vulcanized rubber and is accompanied by little or no heat evolution. Above the 2 per cent sulfur region, a second reaction predominates, forming hard rubber and producing a relatively large quantity of heat. 2. The presence of an accelerator (Santocure) in Buna-S has little, if any, effect on heat of vulcanization. 3. The addition of carbon black to Buna-S lowers the heat of vulcanization in the region above 4 per cent sulfur. The calories evolved in a 10 per cent sulfur compound decrease linearly with percentage of carbon black. 4. The heats of vulcanization of Buna-N (Hycar OR-15) indicate the presence of two chemical reactions. Unlike natural rubber and Buna-S, the ebonite reaction does not predominate until the sulfur concentration is raised above 10 per cent. 5. The heat of vulcanization of Butyl rubber with sulfur is equal to the heat evolved with natural rubber containing 0.6 per cent sulfur. If one sulfur atom reacts per double bond, the maximum amount combining would be 0.72 per cent sulfur. During the vulcanization of Butyl rubber with p-quinone dioxime and lead peroxide, a large amount of heat is evolved by a side reaction between the vulcanizing agents. The reaction involving the Butyl rubber produces about 6 calories per gram, a considerably higher value than the 1 calorie produced by sulfur vulcanization. 6. The heat of vulcanization of Neoprene-GN without added agents corresponds to a value for smoked sheet rubber containing 4.5 per cent sulfur. The addition of zinc oxide and magnesia decreases the heat of vulcanization.

Vulcanization of Butyl Rubber by p-Quinone Dioxime

1978 ◽  
Vol 51 (2) ◽  
pp. 267-277 ◽  
Author(s):  
L. M. Gan ◽  
G. B. Soh ◽  
K. L. Ong
Keyword(s):  
Chemical Reactions ◽  
Crosslinking Density ◽  
Butyl Rubber ◽  
Oxidizing Agent ◽  
Red Lead

Abstract The vulcanization of butyl rubber by p-quinone dioxime oxidized by red lead and tetrachloroquinone was investigated. The maximum physical effective crosslinking density of the vulcanizates appeared to be when p-quinone dioxime and the oxidizing agent were equimolar. The formation of one physical effective crosslink required one molecule of p-quinone dioxime. Chemical reactions are suggested for the vulcanization steps.

A Peroxide Curing Butyl Rubber

1969 ◽  
Vol 42 (4) ◽  
pp. 1147-1154 ◽  
Author(s):  
C. E. Oxley ◽  
G. J. Wilson
Keyword(s):  
Natural Rubber ◽  
Chain Scission ◽  
Butyl Rubber ◽  
Polymer Chains ◽  
The Other ◽  
Cross Linking ◽  
Ethylene Propylene ◽  
Peroxide Curing ◽  
Polymer Reactions ◽  
Crosslinking Reactions

Abstract The reactions of peroxides with polymers have been studied for some time. They form an extensive part of vulcanization technology. Two types of reactions are generally recognized, those leading to crosslinking between polymer chains and those leading to scission of the chains. Natural rubber, polybutadiene and ethylene-propylene rubber are examples of polymers in which crosslinking reactions take place to a greater extent than reactions leading to chain scission and these polymer reactions with peroxides form a useful method of vulcanization. On the other hand, polyisobutene is an example of a polymer which degrades extensively and for polyisobutene and butyl rubber, peroxides have not found use as cross-linking agents.

Biotransformation of Coumarins by Filamentous Fungi: An Alternative Way for Achievement of Bioactive Analogs

2019 ◽  
Vol 16 (6) ◽  
pp. 568-577 ◽  
Author(s):  
Jainara Santos do Nascimento ◽  
João Carlos Silva Conceição ◽  
Eliane de Oliveira Silva
Keyword(s):  
Filamentous Fungi ◽  
Chemical Reactions ◽  
Biological Activities ◽  
Chemical Transformations ◽  
Chemical Structures ◽  
Pattern Structures ◽  
Pharmacological Interest ◽  
Aspergillus Sp ◽  
The Impact ◽  
Related Compounds

Coumarins are natural 1,2-benzopyrones, present in remarkable amounts as secondary metabolites in edible and medicinal plants. The low yield in the coumarins isolation from natural sources, along with the difficulties faced by the total synthesis, make them attractive for biotechnological studies. The current literature contains several reports on the biotransformation of coumarins by fungi, which can generate chemical analogs with high selectivity, using mild and eco-friendly conditions. Prompted by the enormous pharmacological interest in the coumarin-related compounds, their alimentary and chemical applications, this review covers the biotransformation of coumarins by filamentous fungi. The chemical structures of the analogs were presented and compared with those from the pattern structures. The main chemical reactions catalyzed the insertion of functional groups, and the impact on the biological activities caused by the chemical transformations were discussed. Several chemical reactions can be catalyzed by filamentous fungi in the coumarin scores, mainly lactone ring opening, C3-C4 reduction and hydroxylation. Chunninghamella sp. and Aspergillus sp. are the most common fungi used in these transformations. Concerning the substrates, the biotransformation of pyranocoumarins is a rarer process. Sometimes, the bioactivities were improved by the chemical modifications and coincidences with the mammalian metabolism were pointed out.

scholarly journals Physicochemical, Thermomechanical, and Swelling Properties of Radiation Vulcanised Natural Rubber Latex Film: Effect of Diospyros peregrina Fruit Extracts

2013 ◽  
Vol 2013 ◽  
pp. 1-8
Author(s):  
Kazi Md Zakir Hossain ◽  
Nashid Sharif ◽  
N. C. Dafader ◽  
M. E. Haque ◽  
A. M. Sarwaruddin Chowdhury
Keyword(s):  
Natural Rubber ◽  
Natural Rubber Latex ◽  
Tensile Modulus ◽  
Decomposition Temperature ◽  
Latex Film ◽  
Cross Linking ◽  
Rubber Latex ◽  
Swelling Properties ◽  
Fruit Extracts ◽  
Control Film

A range of radiation vulcanised natural rubber latex (RVNRL) films were prepared using various concentrations of aqueous extracts of mature Diospyros peregrina fruit, which acted as a cross-linking agent. The surface of the RVNRL films exhibited an aggregated morphology of the rubber hydrocarbon with increasing roughness due to increasing fruit extract contents in the latex. An improvement in tensile strength, tensile modulus, and storage modulus of RVNRL films was observed with the addition of fruit extracts compared to the control film due to their cross-linking effect. The glass transition (Tg) temperature of all the RVNRL films was found to be at around −61.5°C. The films were also observed to be thermally stable up to 325°C, while the maximum decomposition temperature appeared at around 375°C. The incorporation of fruit extracts further revealed a significant influence on increasing the crystallinity, gel content, and physical cross-link density of the RVNRL films.

Radical Mechanisms in Saturated and Olefinic Systems. II. Disubstitutive Carbon-Carbon Cross-Linking by Tertiary Alkoxy Radicals in Isoprenic Olefins and Rubber

1951 ◽  
Vol 24 (4) ◽  
pp. 777-786
Author(s):  
E. H. Farmer ◽  
C. G. Moore
Keyword(s):  
Natural Rubber ◽  
Cross Linking ◽  
Chain Molecules ◽  
Alkoxy Radicals ◽  
Full Extent ◽  
Carbon Chains ◽  
Butyl Peroxide ◽  
High Degree ◽  
Vulcanization Process

Abstract The high degree of dehydrogenation effected by tert.-butoxy radicals at the α-methylenic groups of olefins enables these radicals to be used for the carbon-to-carbon cross-linking of unsaturated carbon chains, and especially of the polyisoprenic chains of natural rubber. Such cross-linking amounts to a vulcanization process in which the connecting links between chain molecules are just C—C bonds, which may be expected to have appropriate attributes. An examination has first been made of the cross-linking produced by tert.- butoxy radicals (from di-tert.-butyl peroxide) at 140° between the short iso-prenic chains in 1-methylcyclohexene, 4-methylhept-3-ene, 2,6-dimethylocta-2, 6-diene, and digeranyl. Cross-linking proceeds efficiently in each case, and the points of union in these isoprene units which become directly joined are not confined to original α-methylenic carbon atoms. Where the reagent radicals are in considerable deficit, e.g., one per two or three of the isoprene units present, those olefin molecules which are attacked become linked together mostly by single unions to form aggregates containing two, three or four molecules; but in the tetraisoprenic olefins the extent to which more than one union is formed between some of the directly linked molecules becomes appreciable. In natural rubber, cross-linking occurs smoothly and to nearly the full extent corresponding to the (in practice restricted) proportion of peroxidic reagent employed. Good vulcanizates can be so obtained in which the tensile stength is found to increase towards a maximum and then to decline rapidly as the degree of cross-linking steadily increases. Thus to obtain vulcanizates of the optimum physical characteristics, the degree of cross-linking must be suitably chosen. The role of the peroxidic reagent is almost entirely non-additive and non-degradative.

Photoreactions of Nitroso Compounds in Solution. XXI. Stereochemical Course of Photoaddition of Nitrosamines to some Cyclic Olefins and Conformational Isomers Generated by A1,3-Interaction

1972 ◽  
Vol 50 (7) ◽  
pp. 1051-1064 ◽  
Author(s):  
Y. L. Chow ◽  
S. C. Chen ◽  
K. S. Pillay ◽  
R. A. Perry
Keyword(s):  
Steric Hindrance ◽  
Hydrogen Abstraction ◽  
Nitroso Compounds ◽  
Nitroso Group ◽  
Stable Conformer ◽  
Conformational Isomers ◽  
Cyclic Olefins ◽  
Free Radical Attack ◽  
In Trans ◽  
Radical Attack

The results of the photoadditions of N-nitrosopiperidine and N-nitrosodimethylamine to three substituted cyclohexenes are discussed in terms of an "electrophilic" free radical attack of the aminium radicals generated from the photolysis of the nitrosamines. The photoaddition to 4-t-butylcyclohexene gave all four possible oximes; the axial approach of the aminium radical was preferred over the equatorial approach. The photoadditions to 3-methylcyclohexene are highly stereoselective giving oxime pairs 1–2 and 4–5. Both oximes in each pair have 2-amino and 6-methyl substituents in trans-relation; but locked in the alternative conformations through A1.3 interaction of the oximino group. In this addition the aminium radical almost exclusively approaches the C-1 carbon of the most stable conformer from the axial side. The steric hindrance to all possible axial and equatorial approaches to conformers of olefins have been compared. Piperidinium radicals, however, abstract an allylic hydrogen from Δ9,10-octaline since the steric hindrance in the addition process is too great to overcome. The hydrogen abstraction process leads to an intermolecular hydrogen–nitroso group exchange reaction which is similar to that in the photolysis of nitrosamides. A pathway is suggested to account for the generation, insitu, of the heteroannular diene 28 from which oxime 17 could be derived by photoaddition in 1,4-mode.

scholarly journals Modulus of Natural Rubber Crosslinked by Dicumyl Peroxide. I. Experimental Observations

1972 ◽  
Vol 45 (5) ◽  
pp. 1388-1402 ◽  
Author(s):  
L. A. Wood ◽  
G. W. Bullman ◽  
G. E. Decker
Keyword(s):  
Glass Transition ◽  
Natural Rubber ◽  
General Relation ◽  
Quantitative Measure ◽  
Cross Linking ◽  
Rigid Sphere ◽  
Dicumyl Peroxide ◽  
Shear Creep ◽  
Rubber Sheet ◽  
Creep Modulus

Abstract Natural rubber mixed with varying amounts of dicumyl peroxide are crosslinked by heating 120 min at 149° C. The quantitative measure of cross- linking was taken as the amount fp of decomposed dicumyl peroxide, the product of p, the number of parts added per hundred of rubber and f the fraction decomposed during the time of cure. The shear creep modulus G was calculated from measurements of the indentation of a flat rubber sheet by a rigid sphere. The glass transition temperature Tg, was raised about 1.2° C for each part of decomposed dicumyl peroxide. Above (Tg+12) the modulustemperature relations were linear with a slope that increased with increasing crosslinking. The creep rate was negligible except near the glass transition and at low values of fp. Values of G, read from these plots at seven temperatures, were plotted as a function of fp. The linearity of the two plots permits the derivation of the general relation: G=S(fp+B)T+H(fp+B)+A where A, B, H, and S are constants. The lines representing G as a function of fp at each temperature all intersected near the point, fp=0.45 phr, G=2.70 Mdyn cm−2(0.270 MN  m−2). . The constants were evaluated as A=2.70 Mdyn cm−2,B=−0.45 phr, S=5.925×10−3 Mdyn cm−2(phr)−1 K−1 and H=0.0684(Mdyn cm−2) (phr)−1. This equation represented satisfactorily all the data obtained at temperatures from —50 to +100° C for values of fp from about 1 to 24 phr.

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