Cross-linking process of cis-polybutadiene rubber with peroxides studied by two-dimensional infrared correlation spectroscopy: a detailed tracking

Liu, Xifei; Zhou, Tao; Liu, Yongcheng; Zhang, Aiming; Yuan, Canyao; Zhang, Weidong

doi:10.1039/c4ra13502d

Cited by 47 publications

(29 citation statements)

References 44 publications

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“…The amount of addition reactions becomes more significant when cross‐linking of elastomers with butadiene structural units and mainly those with higher amount of 1,2‐butadiene . When there is peroxide cross‐linking of NBR, it is expected that peroxide radicals can react by hydrogen abstraction and also by addition reaction to the double bonds.…”

Section: Resultsmentioning

confidence: 99%

“…27 The amount of addition reactions becomes more significant when cross-linking of elastomers with butadiene structural units and mainly those with higher amount of 1,2-butadiene. [33][34][35] When there is peroxide cross-linking of NBR, it is expected that peroxide radicals can react by hydrogen abstraction and also by addition reaction to the double bonds. In addition to mutual recombination-reactions elastomer radicals, the formed macroradicals can also undergo addition reactions to the double bonds in elastomer chains, thus making the cross-linking process more efficient.…”

Section: Determination Of Magnetic Characteristicsmentioning

confidence: 99%

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Cross‐linking and properties of rubber magnetic composites cured with different curing systems

Kruželák

Chodák

Mošková

et al. 2017

Polymers for Advanced Techs

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Rubber magnetic composites were prepared by incorporation of strontium ferrite into rubber compounds based on acrylonitrile butadiene rubber and ethylene propylene diene monomer rubber. The sulfur, peroxide, and mixed sulfur/peroxide curing systems were introduced as cross-linking agents for rubber matrices. The aim was to investigate the influence of curing system composition on curing process and cross-link density of composite materials. Then, static and dynamic mechanical properties and thermal and magnetic characteristics were investigated in relation to the cross-link density of rubber magnetic composites and structure of the formed cross-links. The changes of dynamical and physicomechanical properties were in close correlation with the change of cross-link density, whereas the tensile strength of magnetic composites showed increasing trend with increasing amount of peroxide in mixed curing systems. On the other hand, thermal conductivity and magnetic characteristics were found not to be dependent on the curing system composition. Incorporation of magnetic crystalline ferrites into various rubber matrices leads to the preparation of magnets, known as ferrite rubber magnets. [5][6][7][8] Rubber magnetic composites are materials that consisted of at least 2 phases, magnetic powder as filler and continuous rubbermatrix. An advantage of these materials is the fact that they are possible to be prepared and processed by the technologies typically used for polymer composites processing. Rubber magnetic composites show excellent flexibility and easy workability, and moreover, they are characterized by good magnetic characteristics. They can be bent, coiled, and shaped without the loss of their magnetic characteristics. Additionally, they are very resistant to corrosion; therefore, no surface treatment is necessary.A lot of vulcanization systems have already been investigated as cross-linking agents for rubber formulations, among which sulfur and peroxide curing systems are still the most frequently used.Sulfur vulcanization is the oldest method used for cross-linking of unsaturated elastomers. It is a complex process that leads to the forming of different types of sulfide cross-links between macromolecules of rubber, namely, monosulfide C-S-C, disulfide C-S 2 -C, and polysulfide cross-links C-S x -C (x = 3-6). In general, sulfur-cured vulcanizates exhibit good tensile properties, high tensile and tear strength, and good elastic behavior, but weak high-temperature stability and poor resistance to aging. 9-13The application of peroxide curing system in cross-linking of elastomers leads to the forming of covalent carbon-carbon crosslinks between elastomer chain segments. C-C bonds have higher dissociation energy in comparison with sulfidic cross-links; therefore, peroxide-vulcanized elastomers exhibit higher thermal stability and good resistance to thermo-oxidative aging. Good electrical properties, low compression set, and no discoloration of the final products are next cognitive features of peroxide cured vulcaniz...

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Section: Resultsmentioning

confidence: 99%

Section: Determination Of Magnetic Characteristicsmentioning

confidence: 99%

Cross‐linking and properties of rubber magnetic composites cured with different curing systems

Kruželák

Chodák

Mošková

et al. 2017

Polymers for Advanced Techs

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“…The main oxidation of SEBS/PP is the research object of the present study. The actual transition region of the SEBS/PP main oxidation can be conveniently determined from the asynchronous PCMW2D FTIR spectra . For an example, two temperature points at 211 and 231 °C are observed in the region of 1840−1640 cm −1 .…”

Section: Resultsmentioning

confidence: 99%

“…The standard procedure is that, the transition point and the transition region of polymers are firstly determined via PCMW2D, and then, the sequential orders of functional groups at a given transition are obtained by generalized 2D analysis. Scientists reported many successful applications of 2D correlation infrared spectroscopy on the study of the mechanism of polymer physical or chemical processes …”

Section: Introductionmentioning

confidence: 99%

Generation Mechanism of Oxidation Products during the Air Atmosphere Oxidation of SEBS/PP Blends: Tracked by 2D Correlation Infrared Spectroscopy

Liu

Zhou

Zhang

2016

Macro Chemistry & Physics

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In this paper, the generation mechanism of oxidation products during the oxidation of the polystyrene‐block‐poly(ethylene‐co‐1‐butene)‐block‐polystyrene copolymer (SEBS)/poly(propylene) (PP) blend in air atmosphere is investigated using temperature‐dependent FTIR combined with 2D correlation infrared spectroscopy. Differential scanning calorimetry, thermogravimetric analysis, and perturbation‐correlation moving‐window 2D correlation FTIR spectroscopy find three processes associated with SEBS/PP oxidative degradation. The 2D correlation analysis is used to study the sequential order of groups' movement of reactants and oxidation products involved in the main oxidation. It is found that the main oxidation starts from the molecular chains of PP and EB blocks of SEBS. It firstly forms COC structure between the molecular chains of PP and the EB blocks, resulting in the cross‐linked structure. Aliphatic ketones are formed via the β‐scission of the main chains of PP or the EB blocks. Then, aliphatic ketones are converted into aliphatic esters. After the above reactions, the S blocks of SEBS begin to oxidize. The S blocks are generated into aromatic ketones through β‐scission. The formation of lactones in the molecular chains of PP and EB blocks is followed via the radical biting back. Finally, aromatic ketones generated from the S blocks are converted into aromatic esters through the reactions of Norrish I, the radical coupling, and so on.

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“…Functionalization is further utilized as a reactive compatibilizer to strengthen interfaces between segregated polymer domains. Polybutadiene (PB) was chosen as the elastomer due to its abundance of alkenes, which are able to undergo crosslinking in the presence of radicals . Poly[(3‐(6‐bromohexyl)thiophene)‐ ran ‐(3‐hexylthiophene)] (P3Br x HT, x = 0–1) was chosen as the π‐conjugated polymer where the added bromide group acts to modify polymer packing and doubles as a photoreactive bonding site (Scheme ).…”

Section: Introductionmentioning

confidence: 99%

Enhanced miscibility and strain resistance of blended elastomer/π‐conjugated polymer composites through side chain functionalization towards stretchable electronics

Pakhnyuk

Onorato

Steiner

et al. 2019

Polymer International

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This work presents improved compatibility in an elastomer/π‐conjugated polymer blend through side chain functionalization of the electronic polymer. Poly[(3‐(6‐bromohexyl)thiophene)‐ran‐(3‐hexylthiophene)] (P3BrxHT, x = 0%–100%) was synthesized (i) to improve miscibility with polybutadiene (PB) elastomer through altered π–π interactions and (ii) to covalently bond across phase‐segregated interfaces. Functionalization led to morphology with reduced domain sizes to improve crack onset strain from 7% to 40%. Furthermore, UV‐activated crosslinking reinforced mechanically weak interfaces and yielded at least an additional 40% increase in crack onset strain. Charge mobility in PB/P3BrxHT organic field‐effect transistors showed minimal dependence on bromide concentration and no negative effects from crosslinking. Functionalization was an effective method to reduce brittleness in PB/P3BrxHT blends through morphology modification and crosslinking to improve stability towards strain for potential stretchable electronic applications. © 2019 Society of Chemical Industry

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Cross-linking process of cis-polybutadiene rubber with peroxides studied by two-dimensional infrared correlation spectroscopy: a detailed tracking

Abstract: Detailed mechanism of cis-BR cross-linking with peroxides was studied using PCMD2D and 2D correlation FTIR, and a 5-step process was determined.

Cited by 47 publications

References 44 publications

Cross‐linking and properties of rubber magnetic composites cured with different curing systems

Cross‐linking and properties of rubber magnetic composites cured with different curing systems

Generation Mechanism of Oxidation Products during the Air Atmosphere Oxidation of SEBS/PP Blends: Tracked by 2D Correlation Infrared Spectroscopy

Enhanced miscibility and strain resistance of blended elastomer/π‐conjugated polymer composites through side chain functionalization towards stretchable electronics

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