Mechanical and swelling equilibrium characterization of high cis-1,4-polyisoprene networks

Equilibrium stress-strain relationships in uniaxial extension for high cis-1,4-polyisoprene (Shell IR 307) networks were obtained by extrapolation of relaxation measurements to infinite time through a Bernstein-Kearsley-Zapas (BKZ) constitutive equation. Three series of networks were investigated, each series being characterized by its polymer precursor molecular weight. The influence of cross-linking density was studied through varying amounts of dicumyl peroxide as cross-linking agent. These results were used to test Flory and Erman's recent molecular theory of networks with constraints on junctions. Swelling equilibrium experiments with benzene and cyclohexane were performed on these networks and were in agreement with the mechanical analysis. The polymer-solvent interaction parameter for the system cis-polyisoprene + cyclohexane was estimated to be 0.31 at 20°C in the range 0 to 0.2 of polymer volume fraction.     

Cyclization of synthetic cis-1,4-polyisoprene

Cyclization of synthetic cis-1,4-polyisoprene was carried out by using TiCl₄ and p-toluenesulfonic acid catalyst. The average cyclicity and structure of the polymers cyclized to a different degree was studied by infrared and high-temperature NMR spectroscopy. The methods of synthesizing an average mono-, bi-, tri-, or polycyclic polymer that could be distinguished by high-temperature NMR spectroscopy and followed by gel-permeation chromatography are discussed.     

13C NMR spectroscopic study of epoxidized 1,4-polyisoprene and 1,4-polybutadiene

Partly epoxidized cis- and trans-1,4-polyisoprenes and cis-and trans-1,4-polybutadienes were prepared, and their ¹³C NMR spectra examined. All the prominent resonances in the spectra of the epoxidized polymers were assigned by using lanthanide shift reagent and off-resonance decoupling experiments. A ¹³C NMR method of quantitative assessment of the epoxide content was developed following determination of relative spin-lattice relaxation time (T₁) and nuclear Overhauser effect (NOE) parameters of the various carbons in the epoxidized polyisoprenes and polybutadienes.     

FTIR study of gamma-irradiated cis-1,4-polyisoprene

The effect of γ-irradiation on the structure and oxidation of cis-1,4-polyisoprene is investigated by ATR-FTIR technique. This method provides the valuable insight into the type of oxidation products produced and the extent and nature of intramolecular cyclization and chain scission reactions. The formation of ketones, alcohols and/or ethers, and hydroperoxides is apparent already at small doses of γ-radiation and it increases with the exposure time significantly. At the highest dose of 309 kGy a decrease in the intensity of C=O stretching mode of ketones (1717 cm⁻¹) was observed while the overall area of the band remained the same as in the case of 188 kGy dose. The shoulders observed at 1740 cm⁻¹ and 1772 cm⁻¹ could be assigned to C=O stretching frequency of esters and five-membered-ring lactones, respectively. Higher doses of γ-radiation also cause the formation of two relatively strong bands in the region of conjugated double bonds. These could origin from the aromatic products or cycloenes with one double bond formed by cyclization and chain scission processes.     

Normal coordinate analysis of cis-1,4-polybutadiene

The fundamental vibrational frequencies of an isolated chain of cis-1,4-polybutadiene have been calculated. Infrared and polarized Raman data are used in the force constant refinement routine. The assignments of the vibrational frequencies are discussed in terms of the potential energy distribution.     

NMR relaxation study of crosslinked cis-1,4-polybutadiene

Proton relaxation measurements have been used to investigate the effects of crosslinking on the segmental motion in cis-1,4-polybutadiene samples. The temperature dependence of proton spin–lattice relaxation time T₁ and spin–spin relaxation time T₂ at 60 and 24.3 MHz are reported in cis-1,4-polybutadiene (PB) samples with different crosslink density including uncrosslinked PB and samples with 140, 40, and 14 repeat units between crosslinks. In addition, spin-lattice relaxation times in rotating coordinate frame, T_1p, have also been determined. The relaxation data are interpreted in terms of the effects of crosslinks on segmental chain motions. Because of their sensitivity to low-frequency motion, T₂ data are of major interest. At temperatures well above the T₁ minimum the small T₂ temperature dependence resembles solidlike behavior reflecting the nonzero averaging of dipolar interactions due to anisotropic motion of the chain segments between crosslinks. The magnitude of T₂ at 60°C is found to be proportional to the average mass between crosslinks.     

Sorption and addition of bromine from aqueous solutions on cis-1,4-polyisoprene

The sorption of bromine from bromine water on cis-1,4-polyisoprene film and the initial stages of bromination are studied at concentrations of 0.002–0.1 mol/l and temperatures of 15–35°C. The diffusion coefficient of bromine into natural rubber (NR) is 1.3–2.0 × 10^?6 cm²/sec for the total sorption and 5–13 × 10^?7 cm²/sec for the irreversible sorption. The partition coefficient of bromine between water and rubber increased from 17.3 at 15°C to 37.1 l/kg at 35°C. The chemical potential, enthalpy and change in entropy of partition are, at 25°C, respectively: ?1.9 kcal/mol, 6.6 kcal/mol and 28.4 cal/mol. K. The irreversible sorption is due to a charge-transfer complex between bromine molecules and double bonds of the rubber. The complex is the first stage of the addition reaction, which becomes noticeable at concentrations above 0.012 mol/l. With increasing bromine concentration the concentration of the complex decreases and the added bromine increases. The charge transfer complex appears to change the conformation of the cis-NR chains so that the bromine addition occurs in the trans-conformation, as shown by FT–IR spectra. The bromination is accompanied by a marked crystallization effect as illustrated by thermal analysis and WAXS measurements.     

NMR measurements on cis-1,4-polybutadiene as a function of pressure

Measurements are reported of the nuclear spin—lattice relaxation time T₁ in cis-1,4-polybutadiene at room temperature up to a pressure of 3,500 bar. Up to 2,000 bar the relaxation curves are described by a single T₁, the pressure variation of which indicates, in the Arrhenius model, an activation volume of 14.5 cm³ mole^?1. Above 2,000 bar the effects of strain due to partial crystallization become evident, and multiple relaxation is observed. By measuring the compressibility of this material up to 10 kbar an estimate of the free volume is made, giving with P in kbar. This measurement is applied in turn to two models of the glassy state, that of Cohen and Turnbull¹ which yields an activation volume of 84 cm³ mole^?1, and that of Adam and Gibbs,² which leads to a critical configurational entropy of 7.7 k_B. In the liquid state the transverse nuclear relaxation, measured by the spin-echo technique, appears to be governed by the same process as T₁.     

DSC and FTIR study of the gamma radiation effect on cis-1,4-polyisoprene

The effect of γ-radiation on the cis-1,4-polyisoprene in the presence of oxygen is investigated by ATR-FTIR technique and non-isothermal DSC measurements. FTIR measurements have shown that the formation of hydroperoxides, ketones, alcohols and/or ethers is apparent already at lower, 20–50 kGy, doses of γ-radiation and it increases significantly with the exposure time. Besides, lactones, anhydrides, peresters, carboxylic acids, and esters are formed, too. Spectral changes in the region of C=C conjugated double bonds indicate a formation of shorter polyene structures and aromatic rings. Kinetic parameters describing the temperature dependence of the induction period have been obtained from DSC measurements using the isoconversional method. Residual stabilities have been calculated in order to characterize the gamma radiation effect on polyisoprene thermooxidative stability. Both methods proved that doses lower than 50 kGy do not cause severe changes in polymer properties.     

Thermo-oxidative aging in surface layer of cis-1,4-polybutadiene vulcanizates

A study of the microstructural changes occurring in the surface layer of cis-1,4-polybutadiene (BR) vulcanizates during thermo-oxidative aging in the temperature range of 120–180°C was carried out by using optical microscope, SEM, MIR–IR, XPS, and swelling. The physical properties, structural changes, and interreaction between rubber and filler (clay) in the surface layer comparing with the center bulk of BR vulcanizates are observed.     

Effect of carbon black on the thermal properties and flammability of cis-1,4-polyisoprene vulcanizates

The effect of carbon black with various particle sizes and specific surfaces on the thermal properties of the sulphur vulcanizates ofcis-1,4-polyisoprene was studied by means of thermal analysis. It was found that the addition of carbon black does not change the nature of the thermal processes in isoprene rubber vulcanizates essentially, but it distincly affects the positions of the peaks recorded in the DTA curves. The specific surface of carbon black affects the temperature of the first exothermic process and the temperature and rate of destruction of cross-linked polyisoprene. The presence of carbon black brings about a reduction in the flammability ofcis-1,4-polyisoprene vulcanizates. The specific surface of carbon black influences the value of the oxygen index OI.

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Zusammenfassung Mittels Thermoanalyse wurde der Einfluß von Ruß mit unterschiedlicher Partikelgröße und unterschiedlicher spezifischer Oberfläche auf die thermischen Eigenschaften von Schwefelvulkanisaten von cis-1,4-Polyisopren untersucht. Es wurde festgestellt, daß die Zugabe von Ruß die thermischen Vorgänge in Isoprengummivulkanisaten nicht wesentlich verändert, daß jedoch die Lage der in den DTA-Kurven aufgezeichneten Peaks eindeutig beeinflußt wird. Die spezifische Oberfläche von Ruß beeinflußt die Temperatur des ersten exothermen Vorganges sowie Temperatur und Geschwindigkeit von Abbau des vernetzten Polyisoprenes. Die Gegenwart von Ruß führt eine Verminderung der Entflammbarkeit voncis-1,4-Polyisopren-Vulkanisaten herbei. Die spezifische Oberfläche von Ruß beeinflußt den Wert der Sauerstoffzahl.

     

Functionalization of cis-1,4-polyisoprene using hypervalent iodine compounds with tetrazole ligands

Hypervalent iodine(III) compounds with tetrazole ligands C₆H₅I(N₄CR)₂ (R  CH₃, C₆H₅, 4-CH₃C₆H₄) reacted, in the presence of elemental iodine, with the double bonds in cis-1,4-polyisoprene (polyIP) to afford iodo-tetrazolylated polymers. The alkyl-iodide groups in the products of the polyIP functionalization were utilized as macro chain-transfer agents for the iodine-transfer polymerization of methyl methacrylate, which yielded brush polymers with well-defined poly(methyl methacrylate) side chains. In addition, the iodo-tetrazolylated polymers were reacted with NaN₃ in DMF at room temperature, and it was noticed that, in addition to nucleophilic substitution, elimination reactions took place. However, the presence of azide groups was taken advantage of and successful click chemistry-type of grafting-onto reactions were carried out with alkyne-capped poly(ethylene oxide) in the presence of CuBr and N,N,N′,N″,N″-pentamethyldiethylenetriamine. The thermal decomposition of both the iodo-tetrazolylated and the azido-tetrazolylated polymers was exothermic, especially for the latter materials. © 2019 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58, 172–180     

The thermal behaviour of cis-1,4-polyisoprene in the presence of cobalt salt

The effects of synthetic fatty acids (Versatic 10, average formula C₁₁H₂₂O₂) and the cobalt salts of these acids (cobalt siccative) on the thermal properties of cis-1,4-polyisoprene were examined, using a rheometer and a derivatograph. It was found that both Versatic 10 and the cobalt siccative accelerate the peroxide vulcanization of the isoprene rubber considerably, simultaneously decreasing the cross-linking density and increasing the sol fraction content in the vulÇanizates. This is brought about by parallel radical and ionic decomposition of the peroxide initiator in the presence of these compounds. The addition of Versatic 10 or the cobalt siccative to the polyisoprene rubber does not alter the general character of its thermal changes, but decreases the temperatures of these processes and the degradation degree of the elastomer.

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Zusammenfassung Der Einfluss synthetischer Fettsäuren (Versatic 10, mittlere Summenformel C₁₁H₂₂O₂) und ihres Kobaltsalzes (Kobalt-Sikkativ) auf die thermischen Eigenschaften von cis-1,4-Polyisopren wurde mittels Rheometer und Derivatograph untersucht. Sowohl Versatic 10 als auch das Kobaltsikkativ beschleunigen die Peroxid-initiierte Vulkanisation des Isoprenkautschuk, gleichzeitig wird die Vernetzungsdichte verringert und der Gehalt an löslichen Stoffen in den Vulkanisaten erhöht. Ursache dafür ist der parallelle Ablauf der radikalischen und ionischen Zersetzung des Peroxids in Gegenwart der Zusätze. Die Beimengung von Versatic 10 oder Kobaltsikkativ zum Polyisoprenkautschuk ändert nicht den allgemeinen Charakter der thermischen Umwandlungen, aber die Temperatur dieser Reaktionen und der Abbau des Elastomeren werden verringert.

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, C₁₁H₂O₂ ( 10) -1,4-. , 10, , . . 10 , , .

     

Antagonistic effects of hindered piperidines and organic sulphides in photostabilization of cis-1,4-polybutadiene

The photostabilizing properties of the mixtures of organic sulphides (2,2′-thiobis(4-methyl-6-tert-butylphenol); bis-(4-hydroxyphenylene) sulphide; thio-oligomer of hydroxyphenylene sulphide; bis [β-(3,5-di-tert-butyl-4-hydroxybenzyl)-methylcarboxyethyl] sulphide; dilaurylthiodipropionate) and hindered piperidines (bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate; 4-hydroxy-2,2,6,6-tetramethylpiperidino-1-oxy; 2,2,6,6-tetramethylpiperidine) in photostabilization of cis-1,4-polybutadiene have been studied by using IR, ESR and TLC methods. A mechanism for antagonistic effects between these two types of stabilizers has been proposed.