Study of Ozonated Olive Oil: Monitoring of the Ozone Absorption and Analysis of the Obtained Functional Groups

The peculiarities of ozone absorption during olive oil ozonolysis have been studied by continuous monitoring of ozone concentrations at the bubbling reactor outlet. The determined amount of ozone, consumed during the ozonolysis of the double bonds, was used as alternative way for evaluation of the degree of unsaturation of the oil. The basic functional groups, products of the reaction: ozonides and aldehydes have been quantitatively characterized by means of ¹H-NMR spectroscopy, whereupon their ratio was found to be 93.4:6.6 (mol. %), respectively. The determined ratio between the cis and trans ozonides was 46:54.     

Ozone cracking and flex cracking of crosslinked polymer blend compounds

Ozone cracking and flex cracking of crosslinked elastomer blends of brominated isobutylene/para‐methylstyrene copolymer (BIMSM) and unsaturated elastomers, such as polybutadiene rubber (BR) and natural rubber (NR), are studied. This saturated BIMSM elastomer, which is a terpolymer of isobutylene, para‐bromomethylstyrene, and para‐methylstyrene, functions as the ozone‐inert phase of the blend. Ozone cracking is measured by the failure time of a tapered specimen under a fixed load in a high severity ozone oven, whereas flex cracking is ranked by the De Mattia cut growth. The ozone resistance of BIMSM/BR/NR blends is compared to that of a BR/NR blend (with or without antiozonant) at constant strain energy densities. The effects of the BIMSM content in the blend, the structural variations of BIMSM, and the network chain length between crosslinks on these two failure properties, which are important in crosslinked compounds for applications in tire sidewalls, are discussed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2183–2196, 2007     

Ozonation of sunflower oil: Spectroscopic monitoring of the degree of unsaturation

Consumption of ozone by unsaturated FA moieties of sunflower oil (SFO) was monitored by ¹H NMR and FTIR spectroscopy. Degradation of linoleate was found to be 1.5 and 1.8 times higher than oleate when SFO was ozonized in the absence and presence of water, respectively. Products of ozonation in both cases include aldehydes and ozonides with 1,2,4-trioxolane ring. Hydroxyl-containing compounds, which could be carboxylic acids and/or hydroperoxides, were also detected in samples ozonized in the presence of water. The extent of ozonation had very little effect on the aldehyde/ozonide ratio obtained from NMR spectra, especially in the ozonation of neast SFO. The aldehyde/ozonide ratios obtained regardless of the extent of ozonation were 10.5:89.5 and 46.6:53.4 for SFO ozonized in the absence and presence of water, respectively.     

The influence of Ni/Nd‐based Ziegler–Natta catalyst on microstructure configurations and properties of butadiene rubber

Neodymium (Nd)‐based Ziegler–Natta catalyst has been well known for preparing polybutadiene rubber (BR) containing high, about 98%, cis−1,4 configuration with extremely low gel content providing superior resistance to low‐temperature fatigue and abrasion. However, its cost is more expensive than a conventional nickel (Ni)‐based catalyst. The Nd‐BR has poor processability with high cold flow due to its high linearity and molecular weight. To compare with a traditional process, the BR produced by Ni‐based catalyst has higher level of branching resulting in the better processability, but it contains medium amount of gel. To balance the catalyst cost and the BR properties, this article reported the influence of a solution containing Ni‐ and Nd‐based Ziegler–Natta catalyst (Ni/Nd) using diethyl aluminum chloride and triethyl aluminum as co‐catalysts on 1,3‐butadiene (BD) conversion and physical properties of the elastomeric materials based on obtained rubber (Ni/Nd‐BR). In the presence of toluene, the increase in the Ni/Nd molar ratio from 0.0/1.0 to 0.4/0.6 yielded Ni/Nd‐BR containing cis−1,4 units of 95%–96% with significantly decreasing both levels of vinyl−1,2 and trans−1,4 configurations from 0.26% to 0.13% and 4.44% to 3.07%, respectively. When cyclohexane was applied as the reaction media, 100% BD conversion was achieved and the Ni/Nd‐BR had very low content of vinyl−1,2 unit (0.07%). The mechanical properties in terms of tensile properties and abrasion resistance of the elastomer based on Ni/Nd‐BR having high cis‐1,4 and relatively higher trans−1,4 configurations were superior to elastomers based on commercial BRs produced by using Ni‐ and Nd‐based catalyst systems. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41834.     

Microstructure analysis of brominated styrene–butadiene rubber

The bromine addition to the SBR double bonds in chloroform at 0°C has been investigated by FTIR, ¹H NMR and DSC techniques. In this case, bromine molecules react exclusively with the polydiene double bonds and the polystyrene units are unaffected. The bromine reacts preferentially with 1,4‐trans double bonds of the polybutadiene segment of SBR. At low bromination level (below 15%) the bromine reacts mainly with the 1,4‐trans double bonds of SBR, while at higher bromination level (up to 30%) the bromine shows the most reactivity toward the vinylic double bond. Above 30%, the addition reaction occurs on 1,4‐trans double bonds. The microstructure of modified and unmodified styrene–butadiene copolymers were fully characterized by ¹H NMR technique. Expanded regions have been utilized to resolve the complex ¹H NMR spectrum and establish the compositional and configurational sequences of styrene–butadiene copolymers. POLYM. ENG. SCI., 47:87–94, 2007. © 2007 Society of Plastics Engineers     

1H NMR Study of Methyl Linoleate Ozonation.

Unsaturated fatty acids are essential components of vegetable oils and cellular membranes and the involved aspect of unsaturated fatty acids ozonation have been widely studied by different authors. In this paper, in vitro ozonolysis of unsaturated fatty acids with addition of water or ethanol has been studied by Proton Nuclear Magnetic Resonance (¹H NMR) at 250?MHz in order to explore the possibility of this technique for the detection of Criegee ozonides in characterizing ozone reaction with these substrates. The ozonolysis of methyl linoleate showed that signal intensities from formed ozonides were increased with ozone concentration increments. However, the signal intensities with addition of water were higher than those in ethanol addition. Signal intensities from olefinic double bonds were found to decrease with the increment in ozonide signals. Thus, a correspondence of the behavior of these signals is observed with a proportional rate reaction between the number of double bonds in the substrate molecule. Signals from aldehyde formation were poorly detected at lower ozone concentration. It was concluded that the evaluation of ozonide and olefinic double bond signals from 250?MHz ¹H NMR can be a useful tool in assessing ozone reaction with biomolecules. The reaction mechanism for the ozone reaction with unsaturated fatty acids in the presence of water or ethanol is analyzed.     

High-temperature degradation of butadiene-based model elastomers by reactive molecular dynamics simulation

Thermal degradation of butadiene-based model elastomers was analyzed via a novel reactive molecular dynamics simulation (ReaxFF) method. The molecular simulation was carried out on 40 monomer units connected together. Degradation pathways of both homopolymer and copolymer of butadiene-based model elastomers such as polybutadiene (BR) and poly (styrene-co-butadiene) (SBR) were studied. The evolution of different fragmented products was examined as a function of time and heating rate. The formation mechanisms of different degraded fragments were visualized via the simulation method. The major decomposition products obtained from these model compounds were the monomers and comonomers. Pyrolysis gas chromatography–mass spectrometry (py-GC–MS) analysis was performed on the commercial samples of BR and SBR to verify the simulation results. The results obtained from the reactive simulation were very consistent with the experimental results. The activation energy required for the thermal decomposition of butadiene-based model elastomers were calculated both from the ReaxFF simulation and thermogravimetric analysis (TGA). The results were also in good agreement. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48592.     

1,3‐butadiene polymerization using Co/Nd‐based Ziegler/Natta catalyst: Microstructures and properties of butadiene rubber

Among Ziegler‐Natta catalysts used for 1,3‐butadiene (1,3‐BD) polymerization, the advantage of a neodymium (Nd)‐based catalyst is that it provides butadiene rubber (BR) with a high content of cis?1,4 configuration and a low amount of vinyl?1,2 units. Whereas, a cobalt (Co)‐based catalyst can produce BR with a low content of trans?1,4 configuration. Thus, this research was aimed to prepare BR containing a high content of cis?1,4 configuration with low amounts of both trans?1,4 and vinyl?1,2 units using a combination of Nd‐ and Co‐based Ziegler/Natta catalysts with triethyl aluminum (TEAL) and diethyl aluminum chloride (DEAC) acting as a co‐catalyst and a chlorinating agent, respectively. The effects of the molar Co/Nd ratio, TEAL concentration, DEAC loading, 1,3‐BD content, solvent type, and reaction temperature on % conversion, microstructures, molecular weight, and molecular weight distribution of the obtained BR (Co/Nd‐BR) were evaluated. The Co/Nd‐BR having >97% of cis?1,4 configuration, <2% of trans?1,4 structure, and <1% of vinyl?1,2 unit with >80% conversion was achieved when 3.01 M of 1,3‐BD concentration was treated in a toluene/cyclohexane mixture (7/3 [w/w]). The Co/Nd‐BR exhibited no gel formation with high mechanical performance, which was equivalent to commercial BR produced from a Nd‐based catalyst system. POLYM. ENG. SCI., 55:14–21, 2015. © 2014 Society of Plastics Engineers     

Ozone-mediated polyol synthesis from soybean oil

Polyols from vegetable oils can replace petroleumbased polyols in the preparation of polyurethanes and polyesters in a wide range of applications. However, previous preparation methods are either too costly, inefficient, or yield secondary alcohols, which are less reactive than the desired primary alcohols. The objectives of this study were to prepare primary soy-based polyols by a new catalytic ozonolysis process and to characterize the composition of the product mixture. In this new process, the polyols were prepared by passing ozone through a solution of soybean oil and ethylene glycol in the presence of an alkaline catalyst. Unlike conventional ozonolysis that yields aldehydes and carboxylic acids by spontaneous decomposition of the ozonide intermediates, the ozonides in our method reacted with the hydroxyl group of the glycol to form an ester linkage with a terminal hydroxy group. Statistical analysis of the product mixture indicates that the resulting polyol mixture is more uniform than the original TG mixture, having (2-hydroxy)nonanoate as the major component of the new hydroxyl functional TG. The chemical structure of the polyols produced was further characterized by iodine number and ¹³C NMR and FTIR spectroscopy, which confirmed the cleavage of the double bonds, the presence of hydroxyl groups, and the formation of new ester linkages.     

Synthesis of a high‐trans 1,4‐butadiene/isoprene copolymers with supported titanium catalysts

The copolymerization of butadiene (Bd) and isoprene (Ip) with a supported titanium‐triisobutyl aluminum catalyst system was studied. An analysis using differential scanning calorimetry, X‐ray diffraction, and ¹³C‐NMR spectra indicated that products with 25–60 mol % Bd units were random copolymers and that the melting temperatures and glass‐transition temperatures (Tg) were 30–40 and ?74°C (or thereabout), respectively, which were very similar to those of natural rubber. The chemical structure of these copolymers was characterized by a high‐trans 1,4‐configuration: the trans 1,4‐content of Ip units was greater than 98%, and the trans 1,4‐content of Bd units was greater than 90%. The reactivity ratio of Bd was greater than that of Ip (r_Bd = 5.7 and r_Ip = 0.17). The sequence distribution of the monomer units of the copolymers followed a first‐order Markov statistical model. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1800–1807, 2003     

Microstructure‐thermal property relationship of high trans‐1,4‐poly(butadiene) produced by anionic polymerization of 1,3‐butadiene using an initiator composed of alkyl aluminum,n‐butyl lithium,and barium alkoxide

This article deals with the characterization of high trans‐1,4‐poly(butadiene) (TPBD) prepared by means of an anionic polymerization using an initiator composed of alkyl aluminum, n‐butyl lithium, and barium alkoxide. By controlling both initiator composition and polymerization temperature, a set of TPBD was prepared with well‐known number of 1,4‐trans units, molecular weight distribution, and average molecular weight. Analyses by differential scanning calorimetry and diffraction of wide‐angle X‐rays showed a direct relationship between the microstructure of the polymer and its thermal properties. By increasing the number of 1,4‐trans units (70–90%), the crystallinity of the polymer was increased (10–30%); polymers with less than 65% of 1,4‐trans units were amorphous, whereas TPBD with a number of 1,4‐trans units greater than 80% were polymorphous and presented two endothermic transitions. Summing up, the results presented in this article indicate that cyclohexane solutions of alkyl aluminum, n‐butyl lithium, and barium alkoxide allow produce polybutadienes with enough amount of 1,4‐trans units to display a regular microstructure that makes them susceptible to experience‐induced crystallization, likewise at a reaction rate similar to that observed for the commercial production of poly(butadiene) with n‐butyl lithium. POLYM. ENG. SCI., 2009. © 2008 Society of Plastics Engineers     

Studies on thermodynamic compatibility of nitrile rubber and polybutadiene by inverse gas chromatography

Inverse gas chromatography technique has been used to study the thermodynamic compatibility of the industrially important elastomers polybutadiene (BR) and polybutadiene copolymerised with acrylonitrile (NBR). The NBR used in this study had nitrile contents of 18 and 34%. The ratio of BR/NBR in blends varied between 1 and 0.25 in both cases and retention volume of twelve probes was measured at 80°C. The Flory-Huggins interaction parameter X′₂₃, computed using a standard procedure, and also the interaction parameter B₂₃ showed that BR and NBR are incompatible in all compositions and that incompatibility increases with nitrile content. © 1995 John Wiley & Sons, Inc.     

DSC study of thermal decomposition of partially ozonized diene rubbers

The thermal decompositions of partially ozonized 1,4-cis-polybutadiene (E-BR), 1,4-cis-polyisoprene (E-IR), 1,4-trans-polyisoprene (Z-IR), 1,4-trans-polychloroprene (Z-PCh), and of polybutadiene elastomer (BR) (microstructure: 1,4-cis, 47%; 1,4-trans, 42%; 1,2, 11%) were studied. The respective thermograms were described by the presence of an intense and relatively broad exothermic peak in the 60–200°C range, which is the result of thermolysis of functional groups of the peroxide type. The measured values of the enthalpy of the reaction, normalized with respect to the amount of reacted ozone (kJ/mol O₃), were as follows: 337 (E-BR), 260, (BR), 197 (E-IR), 180 (Z-IR), and 239 (Z-PCh). Values of the activation energy and reaction order were also determined: 122.6, 118.5, 108, 113, 101.5 and 1.0, 0.96, 1.04, 1.08, and 1.25, respectively. The enthalpy values, obtained by means of differential scanning calorimetry, should be used for quantitative determination of ozonides from polydienes and polyisoprenes. © 1996 John Wiley & Sons, Inc.     

Retardation of cold flow in immiscible rubber blends by tailoring their microstructures

Cold flow is a well‐known characteristic and also an unresolved drawback for uncured rubber materials. In this paper, a simple approach of retarding the cold flow of cis‐1,4‐polybutadiene rubber (BR) elastomer is reported by controlling the phase separation and crystallization that occurs in immiscible BR/trans‐1,4‐polyisoprene (TPI) blends. The BR/TPI blends showed an untypical phase diagram below 150 ^oC. Upon crystallization the amorphous BR facilitates the nucleation of TPI. The higher the BR content is, the less the surface roughness of the TPI crystals, and then a larger dendritic pattern that resulted from the cold flow of BR was observed in the microstructure. BR/TPI blends with the highest resistance to cold flow were obtained by optimizing the composition and thermal treatment in such a way that small soft amorphous BR domains were entrapped in the rigid TPI crystalline phase. It is expected that this study could provide a simple way for the prevention of cold flow of rubber materials. © 2017 Society of Chemical Industry     

Styrene–butadiene block copolymer with high cis‐1,4 microstructure

The sequential block copolymerization of styrene (St) and butadiene (Bd) was carried out with an activated rare earth catalyst composed of catalyst neodymium tricarboxylate (Nd), cocatalyst Al(i‐Bu)₃ (Al), and chlorinating agent (Cl). The microstructure, composition, and morphology of the copolymer were characterized by FTIR, ¹H NMR, ¹³C NMR, and TEM. The results show that styrene–butadiene diblock copolymer with high cis‐1,4 microstructure of butadiene units (～ 97 mol %) was synthesized. The cis‐selectivity for Bd units was almost independent on the content of styrene units in the copolymer ranging from 18.1 mol % to 29.8 mol %. The phase‐separated morphology of polystyrene (PS) domains of about 40 nm tethered by the elastomeric polybutadiene (PB) segments is observed. The PS‐b‐cis‐PB copolymer could be used as an effective compatilizer for noncompatilized binary PS/cis‐PB blends. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Further study on the one-pot synthesis of (E)-2-nonenal from castor oil

A one-step procedure is described for the synthesis of (E)-2-nonenal from commercial castor oil by ozonolysis in methanol, followed by reduction of the ozonide products with dimethyl sulfide and exposure of the resulting intermediate product to dilute sulfuric acid. The developed process allows the production of the aldehyde with a yield of 80% at a purity of 95%. The method has advantages over all those reported earlier, because of inexpensive raw material and reducing agent, recycling of the solvent and its unusual simplicity.     

Ozonolysis of cyclododecene

Ozonolysis of cyclododecene was carried out to produce an w-formyl carboxylic acid (12-oxododecanoic acid) which is derived from zwitterion and aldehyde moiety that are formed during the reaction. The ozonolysis was performed to examine the product distribution under such reaction variables as temperature, kinds of solvent, and presence of catalyst. The yield of polymeric ozonide, which is undesirable product, was measured to be dominantly 86% without pyridine catalyst, whereas, only 10.25% with the catalyst. The optimum reaction condition was to be in MC (methylene chloride) solvent, and in the presence of equimolar olefin and pyridine catalyst at O°C, at which the yields of polymeric ozonide, 1,12-dodecanedialdehyde, 1,12-dodecanedicarboxylic acid, and 12-oxo-dodecanoic acid were 10.25%, 26.72%, 26.31%, and 36.72%, respectively.     

高顺式1,4-聚丁二烯/高间同1,2-聚丁二烯共混物的力学性能

研究了镍系高顺式１,４－聚丁二烯与钴系高间同１,２－聚丁二烯二元共湿物的生胶性能和硫化胶性能。结果表明,随着共混胶中间同１,２－聚丁二含量分数为４％时,共混胶不冷流。当间同１,２－聚丁二烯质量分国８％时,共混胶加工性能与ＢＲ９０００接近,硫化胶３００％定伸应力较ＢＲ９０００提高３ＭＰａ,伸长率为４６０％并显示出较好的综合性能。     

The effect of heat history on thermal degradation of elastomers containing butadiene units

The aim of this research is to develop a new method for studying thermal degradation behavior of elastomers containing butadiene units by isothermal and anisothermal analysis. Accelerated aging such as isothermal thermogravimetry analysis shows that when BR, SBR and NBR elastomers are subjected to specific time and temperature condition in nitrogen atmosphere, an interchain reaction occurs. Experimental observations also show that thermal degradation mechanism of these elastomers depends on heating rate and time–temperature history. For these types of elastomers, the effect of time is similar to temperature and time–temperature superposition principle can be employed for studying the thermal degradation mechanism of elastomer containing butadiene units. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009