Chemical initiation mechanism of maleic anhydride grafted onto styrene-butadiene-styrene block copolymer

The mechanism of grafting styrene-butadiene-styrene (SBS) tri-block copolymer with maleic anhydride (MAH) initiated by benzoperoxide (BPO) or 2,2^′-azo-bis-isobutyronitrile (AIBN) was studied by FTIR and ¹H NMR spectroscopies. The variation of CC (double bond) content in SBS-g-MAH was used to verify the different graft mechanisms of BPO and AIBN, indicating that the chemical initiation mechanisms of MAH grafted onto SBS of AIBN is different from that of BPO. The graft reaction occurs by addition on CC for AIBN, while by removal of an allylic hydrogen atom from SBS and by addition on CC at the same time for BPO. The graft efficiency of AIBN is higher than that of BPO in this system.     

A study on thermal oxidation mechanism of styrene-butadiene-styrene block copolymer (SBS)

The thermal oxidation process of SBS was studied by in situ FTIR and programming heating up DSC. The thermal oxidation mechanism of SBS was analyzed according to the activation energy and pre-exponential factor calculated by Friedman method. The results show that the oxidation of SBS is mainly on butadiene blocks. It is a self-catalyzed reaction containing four steps. The first step is the initiation of chain by free radical. The second is the growth and decomposition of polymer chain. The third is the formation of anhydride coming from dehydrated carbonyl. The fourth is the annihilation of active centers. Antioxidant which provides H atom easily can annihilate active free radical to protect SBS from thermal oxidation at lower temperature.     

Investigation on properties of polymer modified asphalt containing various antiaging agents

The Styrene–butadiene–styrene copolymer (SBS) triblock copolymer modified asphalt binder (SBSMA), applied in an overlay, and is easy to age in the field. Thus, the thermal aging and ultraviolet (UV) radiations aging of SBSMA must be considered for the research on the performance of asphalt pavement. Antioxidants and UV absorbers were employed to improve the antiaging resistance of SBSMA in this study. The results indicated that the SBSMA with antioxidants has good heat aging resistance, and SBSMA with UV absorbers blends have good photostability. The compound antiaging agents containing antioxidants and UV absorbers are a best choice to prepare SBSMA with better physical and antiaging resistance. The experimental results also indicated that the effects of antiaging agents on the physical properties of SBSMA are little at low contents. Especially conventional physical properties of SBSMA with 1 wt% of ZDDP and 0.5 wt% of UV531 are close to that of SBSMA.     

Depletion mechanism of antioxidants in MDPE-clay nanocomposites under thermal aging

The depletion behavior of two types of hindered phenolic antioxidants (AO), Irganox^® 1010 (I-1010) and Irganox^®1076 (I-1076), in medium density polyethylene (MDPE)/nanoclay composite was evaluated by incubating samples in a forced air oven at 85 °C. The presence of 4 wt% nanoclay accelerated the depletion of both types of AO, particularly at the surface region of the sample. However, the depletion mechanism in the interior of sample was governed by the AO molecular structure. For samples containing the bulky Irganox®1010, OIT decreased exponentially with aging time consistent with a first order reaction. In contrast, an increase of OIT was detected in first 60 days of heat aging for sample containing I-1076 and afterward the OIT decreased slowly with aging time. The hypothesis for the initial increase of OIT is that the relatively small and linear structure of I-1076 may enable it to be trapped inside the nanoclay galleries and then subsequently released into the polymer matrix during heat aging.     

3种分光光度法对天然抗氧化物质抗自由基性能的分析检测

用1,1 二苯基 2 苦基肼(DPPH)自由基捕获、亚硝基R盐 Co3 褪色、连苯三酚红等3种分光光度法对3种野生植物抗氧化剂的对自由基的作用进行了分析检测及方法比较研究。3种分光光度法对自由基的分析检测及抗氧化剂的抗自由基性能检测方法,对于普通实验室检测自由基或相关的研究工作具有很好的实用性。没食子酸丙酯及葡萄籽提取物的抗氧化性要优于灯盏花素提取物。对自由基的清除率可以达到40%～80%,具有很好的抗氧化能力及氧自由基清除作用。     

Effects of ultraviolet radiation, temperature and moisture on aging of coatings and sealants - A chemical and rheological study

Photodegradation of polymeric materials leads to significant modifications in both chemical properties and mechanical-rheological behaviors over time. Thus, it is important to characterize both properties to gain a better understanding of the durability of the materials. In this contribution, the chemorheological tools based upon Fourier transform infrared (FTIR) spectroscopy and dynamic mechanical thermal analysis (DMTA) were used to study the effects of temperature and moisture on photodegradation of a model sealant/coating system based upon a styrene-butadiene-styrene triblock copolymer. Specimens were exposed coincidentally to ultraviolet-visible radiation between 295 nm and 600 nm, and one of four different combinations of temperature and relative humidity (RH), i.e., (a) 30 °C and <1% RH, (b) 30 °C and 80% RH, (c) 55 °C and <1% RH, and (d) 55 °C and 80% RH. The rate of photodegradation was examined in terms of formation of oxidation species and evolution of mechanical-rheological data, including glass transition temperatures, moduli, and the number of effective crosslinked butadiene chains per unit volume per exposure time. Environmental exposure resulted in similar degradation modes for all four environments but the rate of photodegradation was found to depend strongly on temperature. Conversely, the role of moisture on photodegradation was not significant. The study shows that chemical modification can be directly related to the corresponding rheological modifications. In addition, the relative stability of styrene and butadiene against photodegradation as a function of temperature and moisture was compared.     

生物-光度法检测抗氧化剂抗氧化活性

建立了一种测定抗氧化剂抗氧化活性的方法,简称为生物-光度法。考察了吸收光谱、细胞液体积、抗氧化剂和自由基产生体系(混合液)与细胞作用的时间、MTT(四甲基偶氮唑盐)与细胞作用时间等因子对测定结果的影响。实验确定的参数为:2×105mL-1的细胞液100μL、混合液与细胞作用时间15 min,20μL 5 mg/mL MTT与细胞作用时间4 h,测定波长为572 nm。并用该方法测定了葡萄籽提取物等的抗氧化活性。     

Microwave assisted fabrication of polymethyl methacrylate-graphene composite nanoparticles applied for the preparation of SBS modified asphalt with enhanced high temperature performance

In order to improve the high temperature rutting resistance ability and stability of styrene-butadiene-styrene (SBS) modified asphalt, microwave heating emulsion polymerization strategy was used to prepare polymethyl methacrylate (PMMA) and graphene nanoparticles (GNPs) composite (PMMA-GNPs) which was used to prepare PMMA-GNPs/SBS modified asphalt. Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy and thermogravimetric analysis characterizations showed that PMMA-GNPs particles were successfully prepared having a weight ratio of GNPs: PMMA of 1:9. Microwave heating reduced the reaction time from 5 h to 30 min compared to conventional oil bath heating. Dynamic shear rheological test and multi-stress creep recovery test confirmed that 0.06% PMMA-GNPs/SBS modified asphalt (0.06% PMMA-GNPs of the mass of base asphalt) exhibited an increase of 14.2% in elastic modulus (G′), while rutting resistance was enhanced and sensitivity to stress changes was reduced as compared to those of 5% SBS modified asphalt. Fluorescence microscopy analysis and phase separation test revealed that an appropriate amount of PMMA-GNPs can be uniformly dispersed in SBS modified asphalt and enhance the mutual interaction of SBS with base asphalt. Based on the results of mechanical tests and characterizations, a suitable modification mechanism of PMMA-GNPs particles in the original SBS modified asphalt was described in detail. This study proposes a simple, cost effective and fast strategy for the preparation of PMMA-GNPs incorporated SBS modified asphalt and hence can be envisioned of great promise in construction and highway industries.     

Separation and purification of antioxidants from Ampelopsis heterophylla by counter‐current chromatography

In this study, bioactive components from Ampelopsis heterophylla were separated by counter‐current chromatography (CCC). The antioxidant activity of the crude extract was initially evaluated by an online HPLC method. Five compounds in the crude extract exhibited good antioxidant activities, namely, hyperoside ( 1 ), isoquercitrin ( 2 ), rutin ( 3 ), kaempferol‐3‐rutinoside ( 4 ), and quercetin ( 5 ). These compounds were further separated by CCC with biphasic solvent systems and their structures were identified by MS and NMR spectroscopy. All the compounds exhibited significant 1,1‐diphenyl‐2‐picryl‐hydrazyl radical scavenging activities with IC₅₀ values at 18.2 ± 1.3, 17.0 ± 1.4, 24.2 ± 1.2, 38.1 ± 1.7, and 9.0 ± 1.2 μM, respectively. The scavenging ratios of the compounds against hydroxyl radicals were 65 ± 5, 68 ± 4, 96 ± 2, 70 ± 4, and 98 ± 2%, respectively.     

Improving aging resistance of PIM-1 thin films by nano-TiO2 filler used for robust solvent permeation

Polymers of intrinsic microporosity (PIMs) are promising materials for membrane separation because their special rigid and contorted structures contribute to high permeability. However, their chain rearrangement to fill excessive free volume makes the permeability stability a tough challenge. In this work, we report on a new use of rutile nano-TiO₂ to mitigate the physical aging of PIM-1 (a typical PIM) nanofilms for stable permeability by mixing matrix. It was shown that the PIM-1 membrane incorporated with nano-TiO₂ displayed remarkably higher aging resistance with a lower swelling degree in long-term ethanol soaking, having more stable ethanol permeance with only a 5% decrease after 35 days, lower than 25% of the pure one. The mechanism of anti-aging was revealed by molecular simulation, thermal, tensile mechanical, and dynamic mechanical analysis. It was found that nano-TiO₂ had good compatibility with PIM-1 due to strong coordination interaction, making its uniform dispersion in polymer. Additional solvent permeation channels were also created to increase solvent permeance without compromising solute rejection. Due to the reliable interaction of nano-TiO₂, which makes particles serve as physical crosslinking points, the movement of PIM-1 chains was limited partially to mitigate aging, enabling PIM-1-based membranes to have robust solvent permeation.     

Coexisting lamellar phases in water-oil-surfactant systems induced by the addition of an amphiphilic block copolymer

We report here a pioneering study using quadrupolar splitting NMR to detect new phases and phase compositions in the quasi-ternary microemulsion system water-decane-C(10)E(4)/PEP5-PEO5. The striking observation is that at certain compositions the polymer is apparently no longer incorporated into the membranes of the lamellar phase due to space restrictions. The polymer therefore induces a phase separation into two different lamellar phases L(alpha)(1) and L(alpha)(2) such that it fits into L(alpha)(1) while the excess surfactant forms a polymer-free L(alpha)(2) phase.     

Evaluation of two methods for the extraction of antioxidants from medicinal plants

The efficiencies of two traditional extraction methods used in Chinese medicine (the decoction method and the maceration method) were evaluated for the extraction of antioxidants from medicinal plants. A group of medicinal plants possessing nutritious and tonic functions were chosen as model plants. A commonly used extraction method was used as a reference method. The antioxidant capacities and total phenolic contents of the extracts were measured by ferric-reducing antioxidant power and Trolox equivalent antioxidant capacity assays as well as the Folin–Ciocalteu method, respectively. The results obtained indicated that the two traditional extraction methods could effectively extract antioxidants from medicinal plants. These extraction methods can be applied to the analysis and purification of antioxidants in plants, respectively. At home, people can use these methods to extract antioxidants from plants for consumption. In the food industry, these methods could be utilized to prepare crude extracts from plants containing antioxidants for use as food additives. Figure Relation and comparison of extraction efficiencies of two traditional extraction methods with the reference method Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Simulation of free radical addition reactions modified by the presence of cobalt macrocycles

Free radical addition reactions in the presence of cobaloximes and related compounds have been modelled. Several mechanisms are presented and similarities with the “persistent radical effect” noted by Daikh and Finke are discussed. Cobaloximes and salophen

1 System. name: N-acetyl-p-aminophenyl salicylate.

derivatives are widely used in organic synthesis to build carbon-carbon bonds, whereas in polymer synthesis they are used as catalytic chain transfer agents in the production of oligomers. This work shows that these reactions are closely related and also demonstrates the influence that an external radical source has on the overall reaction kinetics.     

A new approach on the thermal stability of SDS copolymer for HMPSA, Part I: Oxidation kinetics for the whole process

The poor aging property of the styrene–diene–styrene (SDS) triblock elastomer copolymer hot-melt pressure-sensitive adhesives (HMPSAs) has raised the importance of research on the aging and anti-aging properties of SDS triblock copolymers, such as styrene–butadiene–styrene (SBS) and styrene–isoprene–styrene (SIS). A mechanistic scheme based on the standard scheme for radical chain oxidation, but taking into account the decomposition of the oxidation-induced peroxide, was built. The kinetic equation of oxygen uptake was deduced from the proposed mechanism, which is composed of a set of reasonable parameters. The relationships among the parameters to induction time, maximum oxygen uptake and the maximum oxidation rate were examined. Numerical simulation methods were established to obtain parameters from the experiment data, by which most kinetic equations of oxygen uptake of the ingredients for HMPSAs were numerically fitted and the relativity of the model to the data was discussed. The study results should prove useful for future studies on the anti-aging performance of other materials.     

SNMS and GDOES studies of the oxidation behavior of TiAl modified by niobium addition

TiAl-based intermetallic alloys are promising candidates as structural materials for high temperature applications. However, industrial application is hindered by insufficient oxidation resistance at temperatures above 700?°C in air. The oxidation resistance can be improved by the addition of ternary and quaternary alloying elements, such as niobium. In several studies it has been demonstrated that this element can reduce the oxidation rate dramatically although the underlying mechanism is not yet fully understood. In the present study the influence of niobium on the high temperature oxidation behavior at 800?°C of Ti-48Al-2Cr was investigated. Niobium was added by alloying as well as by ion implantation. Some specimens were pre-oxidized prior to ion implantation. Thus, it could be demonstrated that niobium is not only active when present in the bulk alloy, but also when located in the initially formed corrosion scale. Moreover, the implantation experiments revealed that the often suggested “doping mechanism” of the titania lattice by Nb⁵⁺ ions cannot play an important role explaining the beneficial effect of Nb. The morphology and composition of the scales formed during oxidation were studied by glow discharge optical emission spectroscopy (GDOES) and secondary neutral mass spectrometry (SNMS). The latter technique was also used in combination with two-stage oxidation experiments using the isotope tracers ¹⁸O and ¹⁵N.     

Investigation of the active species in a Michael addition promoted by chirally modified tetrahydroborate

For the first time, asymmetric 1,4-addition of various malonates to enones has been carried out using tetrabutylammoniumtetrahydroborate (TBATB) in the presence of a chiral ligand. The Michael adducts were formed in reasonably good yields (61-67%) with moderate ee's at 0 °C. ¹¹B NMR spectroscopic studies explain this unexpected reactivity through the predominant formation of an aminodiol modified borate complex in the presence of a hydride acceptor.     

Improving the flame retardancy of polyamide 6 by incorporating hexachlorocyclotriphosphazene modified MWNT

A nitrogen‐, phosphorus‐ and chlorine‐containing flame retardant, hexachlorocyclotriphosphazene (HCTP), has been covalently grafted onto the surface of multi‐wall carbon nanotubes (MWNT) to obtain MWNT‐HCTP. Polyamide 6 (PA6)/MWNT composites were then prepared via melt compounding. The flammability of PA6/MWNT composite was characterized by cone calorimetry, limiting oxygen index (LOI) and UL‐94 tests. The results showed that peak heat release rate of samples containing 3 wt% MWNT‐HCTP was only 460 kW/m², which decreased by 35.2% compared with that of a neat PA6 sample. The LOI value was increased from 22.7% to 26.5%, and UL‐94 test performance was also significantly improved by the presence of MWNT‐HCTP. Scanning electron microscope (SEM) and optical microscope analysis showed that modified MWNT had a better dispersion and compatibility in PA6 than unmodified MWNT. The composition of residue chars and volatile products was investigated by SEM/energy dispersive X‐ray spectroscopy, Fourier transform infrared spectroscopy (FTIR) and thermogravimetric‐FTIR, respectively. It was proposed that grafted HCTP was mainly functioned in the condensed phase, where P, N can synergistically promote char formation and Cl element can catch free radicals to terminate the chain reaction during combustion of the PA6 composite. Copyright © 2014 John Wiley & Sons, Ltd.     

Comparison of various techniques for the extraction and determination of antioxidants in plants

The following extraction techniques have been used for extracting antioxidants (apigenin, coumarin, esculetin, umbelliferone, bergapten, quercetin, rutin, scopoletin and xanthotoxin) from plant material: supercritical fluid extraction, pressurized liquid extraction, extraction by means of Soxhlet apparatus, ultrasonic extraction in ultrasonic bath, and by means of ultrasonic probe. The analytical method based on HPLC?UV detection for the determination of selected antioxidants was developed. For all extracts the antioxidant capacity based on the reduction of free 2,2‐diphenyl‐1 ‐picrylhydrazyl radical was also determined. Comparing all results the ultrasonic probe method using 0.75 g of sample extracted by 50 mL of acetonitrile in water (30%, v/v) for 25 min at room temperature and with amplitude at 60% (equal to 90 W) without pulsation was evaluated as the best tool. The most significant indicator demonstrating this statement is the antioxidant capacity expressed as gallic acid equivalent where the ultrasonic probe method showed the best results in 10 of 16 samples. Also the operability of ultrasonic probe extraction method compared to other tested methods is more favorable.     

Study on the hydrogen donating abilities of benzofuranones as chain-breaking antioxidants using laser flash photolysis technique

The hydrogen donation kinetics of four 3-aryl-benzofuranones with different chemical structures toward tert-butoxyl radicals were studied using laser flash photolysis (LFP) technique. The rate constants of hydrogen reactions, which can be used to evaluate the hydrogen donating abilities of 3-aryl-benzofuranones toward radicals, were obtained. The results showed that the position of substituted methyl group has a very important effect on the hydrogen donating ability of benzofuranone toward tert-butoxyl radicals, i.e. if the methyl group is on 2′-position, the hydrogen donation of 3-aryl-benzofuranone toward tert-butoxyl radicals will be prevented and the hydrogen donating ability will be weakened.