Determination of Double Bonds in Ethylene Propylene Terpolymer Rubbers

1967 ◽  
Vol 40 (3) ◽  
pp. 936-946 ◽  
Author(s):  
R. Hank

Abstract Developments in the field of sulfur vulcanized unsaturated ethylene propylene terpolymer rubbers, also known as EPT rubbers, have progressed rapidly in recent years. Considerable success has been achieved in producing EPT rubbers from ethylene, propylene, and various dienes. Initial difficulties, involving introduction of double bonds into already known ethylene propylene copolymers, were soon overcome when it became clear that it was not the then commonly conjugated dienes such as butadiene and isoprene, but rather nonconjugated dienes, which were required for successful terpolymerization with ethylene and propylene, according to the Ziegler process. As with butyl rubber, it is sufficient, for vulcanization purposes, to incorporate one or two mole per cent of such dienes into the terpolymer. It is especially important, not only for polymerization, but also for rubber processing, to know the type and amount of unsaturation. In this article we wish first of all to report on double bond determinations in general and then, in particular, on qualitative and quantitative dicyclopentadiene determinations in ethylene propylene terpolymers. It is especially important, not only for polymerization, but also for rubber processing, to know the type and amount of unsaturation. In this article we wish first of all to report on double bond determinations in general and then, in particular, on qualitative and quantitative dicyclopentadiene determinations in ethylene propylene terpolymers.

1967 ◽  
Vol 40 (2) ◽  
pp. 563-568
Author(s):  
R. J. de Kock ◽  
A. Veermans

Abstract With the aid of model compounds—derivatives of endo- and exo-dicyclopentadiene—it has been established that a) the 9, 10-double bond (the double bond in the norbornane ring) is involved in the polymerization of dicyclopentadiene with ethylene and propylene, b) dicyclopentadiene, present in the polymerization mixture in the endo-configuration, occurs in the exo-configuration in the polymer chain. The same model compounds enable the dicyclopentadiene content of ethylene propylene dicyclopentadiene terpolymers to be determined by infrared spectroscopic methods. Use is made of the 3045 cm−1 band, which is characteristic of endo-cyclic double bonds in five-membered rings.


1975 ◽  
Vol 48 (5) ◽  
pp. 889-895
Author(s):  
W. Scheele ◽  
S. Fleige

Abstract The results of unaccelerated and accelerated vulcanizations of ethylene-propylene terpolymers (EPDM) demonstrate that the reaction of sulfur with allyl systems (such as those which the 1,5-polyenes contain at concentrations far exceeding the quantity of sulfur introduced for crosslinking purposes) tends toward an order above unity and eventually towards second order, as the sulfur concentration and the double bond content approach the stoichiometric ratio. This could be shown with unaccelerated vulcanizations of EPDM in the absence of ZnO, as well as those accelerated by zinc mercaptobenzothiazole. This is so, in our opinion, because in the one case autocatalysis by the polysulfidic sulfur is inhibited, and in the other it becomes negligible because of the very rapid reaction rate. According to Scheele and Huischen, the reaction order for sulfur decrease for the unaccelerated vulcanization of nitrile rubber is first order, both with respect to time and (very important!) with respect to concentration (nt=no=1), and the reaction is not subject to autocatalysis because of disulfidic crosslinks. Accordingly, we arrive at the conviction, in view of the relations obtained with the EPDM rubbers, that all the rate laws determined for sulfur decrease in 1,5-polyene vulcanizations with an excess of double bonds have as their basis pseudo-reaction orders or pseudo-molecularities. In spite of these generally revealing differences in the kinetics of sulfur decrease and in its chemistry between the 1,5-polyenes with their excess of double bonds and the EPDM rubbers with double bond content that is commensurate with the sulfur concentration, the fact still remains that the reaction of sulfur with polymers containing allyl groups has all the characteristics of a multistep reaction of of catalysis by an intermediate and that these characteristics are obviously those generally found in reactions between sulfur and any kind of compound that contains allyl groups. Even the great differences observed between the chemical constitution and the macromolecular structure of the various homo- and copolymers of the 1,3-dienes (natural rubber and poly butadiene), of polypentenamer, and of the EPDM rubbers under consideration here, cannot alter that circumstance, since each situation involves an analogous reaction of sulfur with the allyl units which sulfur-crosslinkable rubbers contain. Any quantitative differences noted can be attributed to the concentration ratios of all the participating reactants as well as the chemical constitution and reactivity of the allyl units. Thus one cannot escape the conclusion that the submolecular, molecular, and supermolecular structure of the rubbers, as well as the polymerization degree and the molecular weight distribution, are of greater importance for the physical, mechanical, and technological properties of the vulcanizates than the vulcanization itself, which, incidentally, should always be carried out so as to realize optimum technological properties in order to meet the industrial technological requirements.


1965 ◽  
Vol 38 (3) ◽  
pp. 620-626 ◽  
Author(s):  
G. Sartori ◽  
A. Valvassori ◽  
S. Faina

Abstract Monomers (both monoolefinic and diolefinic) containing the bicyclo[2.2.1] heptene system copolymerize with ethylene and propylene by opening the double bond of the endo-methylenic system without rupture of the bicycloheptene system itself. Therefore, only diolefinic monomers produced unsaturated terpolymers. The rate of ethylene-propylene-dicyclopentadiene terpolymerization and the relative reactivity of ethylene and propylene are influenced by the concentration of dicyclopentadiene present in the liquid phase. The rate of vulcanization of ethylene-propylene-dicyclopentadiene terpolymers is slower than that of the other synthetic elastomers (butyl rubber, ethylene-propylene-cyclooctadiene-1,5 terpolymer).


1947 ◽  
Vol 20 (3) ◽  
pp. 627-648
Author(s):  
S. R. Olsen ◽  
C. M. Hull ◽  
Wesley G. France

Abstract 1. When iodine chloride is used for the determination of double bonds in sulfur-vulcanized rubber or GR-S, it undergoes side reactions induced by combined sulfur. 2. Bromine in carbon tetrachloride is believed to give a satisfactory measure of the double bonds in a rubber-sulfur vulcanizate dissolved in dichlorobenzene-chloroform mixture. 3. The relation of one double bond consumed per sulfur atom combined in the rubber-sulfur type vulcanizate was confirmed. 4. Organic accelerators (in the absence of metal activators) catalyze the combination of sulfur without altering the ratio of one double bond loss per sulfur atom combined. 5. The introduction of a metal oxide or soap, such as zinc, causes a different type of vulcanization, which results in less than one double bond consumed per sulfur atom combined. 6. The reactions of propyl sulfide, dodecyl sulfide, propyl disulfide, allyl sulfide, methallyl sulfide, and butylmethallyl sulfide with iodine chloride and with bromine, respectively, are described. 7. The behavior of rubber-sulfur vulcanizates resembles that of butylmethallyl sulfide in reactions with iodine chloride and bromine, respectively; this suggests an alkyl-allyl type sulfur bond. 8. The theory of vulcanization proposed by Armstrong, Little, and Doak, based on the α-methylenic concept of Farmer, is supported by the findings of this investigation.


Polymer ◽  
1975 ◽  
Vol 16 (10) ◽  
pp. 709-713 ◽  
Author(s):  
Yasuyuki Tanaka ◽  
Hisaya Sato ◽  
Yukio Ozeki ◽  
Masaru Ikeyama ◽  
Takefumi Sato

1968 ◽  
Vol 41 (2) ◽  
pp. 400-410
Author(s):  
R. McGuchan ◽  
I. C. McNeill

Abstract A radiochemical technique involving the use of 36C1 has been described previously for the measurement of butyl rubber unsaturations. This method has now been applied to the estimation of the much lower concentration of double bonds present in polyisobutene prepared by the cationic polymerization of isobutene at a low temperature. The nature of the reaction of polyisobutene with radiochlorine in the absence of air is examined, and the experimental results are discussed in relation to present theories of the mechanisms of chain termination in cationic polymerization.


Author(s):  
Alica Bartošová ◽  
Tomáš Štefko

Abstract The aim of the paper was to study and research the application of processing gas chromatographic method for the rapid and accurate determination of the composition of different types of oils, such as substances with the possibility of an adverse event spontaneous combustion or self-heating. Tendency to spontaneous combustion is chemically characterized mainly by the amount of unsaturated fatty acids, which have one or more double bonds in their molecule. Vegetable oils essentially consist of the following fatty acids: palmitic, stearic, oleic, linoleic, and linoleic. For the needs of assessment, the fire hazard must be known, in which the double bond is present, as well as their number in a molecule. As an analytical method, GCMS was used for determination of oils content. Three types of oil were used - rapeseed, sunflower, and coconut oil. Owing to the occurrence of linoleic acid C18:2 (49.8 wt.%) and oleic acid C18:1 (43.3 wt.%) with double bonds, sunflower oil is the most prone to self-heating. The coconut and rapeseed oils contain double bond FAME in lesser amount, and their propensity to self-heating is relatively low.


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