Rare earth metal based DES assisted the VPO synthesis for n-butane selective oxidation toward maleic anhydride

Deep eutectic solvents(DESs) are now considered a new class of ionic liquid analogs that have been generously used in various fields.Herein, vanadium phosphorus oxide(VPO) catalysts are synthesized in combination with a deep eutectic solvent containing rare earth metal(rE-DES), and their catalytic performance in n-butane selective oxidation to produce maleic anhydride(MA) is evaluated. The rE-DES is produced from the interaction of choline chloride(ChCl) and rare earth metal salts(Cerium, Europium, Lanthanum, and Samarium metal salt)(ChCl:rE = 1:0.5–1:3) under mild conditions. It was found that DESs served as structural modifiers and electronic promoters during VPO synthesis. It regulated the chemical state of the catalyst surface, such as the vanadium valence state, acid-base properties, and ratios of V^(4+)/V^(5+),Lat–O/Sur–O and P/V. Various characterization techniques, such as FT-IR, DSC, XRD, SEM, EDS, TEM, Raman, TGA, NH3-TPD, and XPS,were used to examine its physical and chemical characteristics. These characteristics were correlated with the catalytic performance. The VPO catalyst modified by rE-DES showed a significant enhancement of n-butane conversion and MA selectivity while suppressing the selectivity of CO and CO_(2)as well as the CO/CO_(2)ratio compared to the unpromoted VPO catalyst. Especially for Ce-DES-VPO, it increased the n-butane conversion and MA mass yield up to approximately 11% and 10%, respectively. In addition, we evaluated the catalytic performance under different activation atmospheres.

Tetrahedral framework nucleic acids/hyaluronic acidmethacrylic anhydride hybrid hydrogel with antimicrobial and anti-inflammatory properties for infected wound healing

Bacterial resistance and excessive inflammation are common issues that hinder wound healing.Antimicrobial peptides(AMPs)offer a promising and versatile antibacterial option compared to traditional antibiotics,with additional anti-inflammatory properties.However,the applications of AMPs are limited by their antimicrobial effects and stability against bacterial degradation.TFNAs are regarded as a promising drug delivery platform that could enhance the antibacterial properties and stability of nanodrugs.Therefore,in this study,a composite hydrogel(HAMA/t-GL13K)was prepared via the photocross-linking method,in which tFNAs carry GL13K.The hydrogel was injectable,biocompatible,and could be instantly photocured.It exhibited broad-spectrum antibacterial and anti-inflammatory properties by inhibiting the expression of inflammatory factors and scavenging ROS.Thereby,the hydrogel inhibited bacterial infection,shortened the wound healing time of skin defects in infected skin full-thickness defect wound models and reduced scarring.The constructed HAMA/tFNA-AMPs hydrogels exhibit the potential for clinical use in treating microbial infections and promoting wound healing.

Ni/Al_2O_3 catalysts derived from spinel NiAl_2O_4 for low-temperature hydrogenation of maleic anhydride to succinic anhydride

Ni/Al2O3 catalysts were derived from spinel NiAl2O4 with different Ni content ((2.5, 5 and 7.5) wt%). The catalysts were obtained by H-2 reduction and were investigated for the low-temperature hydrogenation of maleic anhydride (MA) to produce succinic anhydride (SA). The characterization results showed that Ni-0 active sites were mainly derived during the H2 reduction from spinel NiAl2O4 Among the catalysts studied, employing the optimum preparation and reaction conditions with Ni(5%)/Al2O3 yielded the highest catalytic performance. A near-100% conversion of MA and similar to 90% selectivity to SA were achieved at 120 degrees C and 0.5 MPa of H-2 with a weighted hourly space velocity (MA) of 2 h(-1). (C) 2017, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

Synthesis and Characterization of a Novel Biomaterial: Maleic Anhydride-modified Poly(dl-lactic acid)

A novel modified poly(dl-lactic acid) (PDLLA) was obtained by covalently grafting of maleic anhydride onto the backbone of PDLLA, attempting to improve PDLLA’s hydrophilicity and cell affinity and to provide reactive groups for further chemical modification. FTIR, 13C NMR and DSC were used to characterize the maleic anhydride-modified PDLLA.

Insights into the thermochemical evolution of maleic anhydride-initiated esterified starch to construct hard carbon microspheres for lithium-ion batteries

Starch,as a typical polysaccharide with natural spherical morphology,is not only a preferred precursor for preparing carbon materials but also a model polymer for investigating thermochemical evolution mechanisms.However,starch usually suffers from severe foaming and low carbon yield during direct pyrolysis.Herein,we report a simple and eco-friendly dry strategy,by maleic anhydride initiating the esterification of starch,to design carbon microspheres against the starch foaming.Moreover,the infuence of ester grafting on the pyrolytic behavior of starch is also focused.The formation of ester groups in precursor guarantees the structural stability of starch-based intermediate because it can promote the accumulation of unsaturated species and accelerate the water elimination during pyrolysis.Meanwhile,the esterification and dehydration reactions greatly deplete the primary hydroxyl groups in the starch molecules and thus the rapid levoglucosan release is inhibited,which well keeps the spherical morphology of starch and ensures the high carbon yield.In further exploration as anode materials for Lithium-ion batteries,the obtained carbon microspheres exhibit good cyclability and rate performance with a reversible capacity of 444 m Ah g^(-1)at 50 m A g^(-1).This work provides theoretical fundamentals for the controllable thermal transformation of biomass towards wide applications.

Solid-Liquid Equilibria of Several Binary and Ternary Systems Containing Maleic Anhydride

Solid-liquid equilibria (SLE) of three binary systems and seventernary systems containing maleic an- hydride (MA) are measured byvisual method. The experimental data are compared with the calculatedones with modified universal quasichemical functional group activitycoefficient (UNIFAC) method in which the interaction parametersbetween groups come from two sources, dortmund data bank (DDB), ifthere's any, and correlations based on our former presentedexperimental SLE data of twenty binary systems.

Ni-loaded Catalyst Containing Activated Clay for Maleic Anhydride Hydrogenation to Succinic Anhydride

In this work, the hydrogenation of maleic anhydride to succinic anhydride in the presence of 5 m%Ni/clay catalysts was investigated. These catalysts were characterized by X-ray diffraction （XRD）, H2 temperature programmed reduction （TPR） and thermogravimetric analysis （TGA） techniques. The XRD and TPR studies showed that Ni was present as Ni2＋ on the support, which indicated that there were no elemental nickel （Ni^0） and Ni203 species in the unreduced samples. Increasing of calcination temperature to 650 ℃ leads to destruction of the support structure observed in TGA, while the catalyst sample calcined at 550 ℃ exhibits better performances than other samples. The ideal conversion of maleic anhydride （97.14%） and selectivity of succinic anhydride （99.55%） were realized at a reaction temperature of 180 ℃ and a weight hourly space velocity of 4 h^-1 under a reaction pressure of 1 MPa.

SYNTHESIS OF MESOPOROUS POLY(STYRENE-co-MALEIC ANHYDRIDE)/SILICA HYBRID MATERIALS VIA A NONSURFACTANT-TEMPLATED SOL-GEL PROCESS

Mesoporous poly(styrene-co-maleic anhydride)/silica hybrid materials have been prepared. The synthesis was achieved by the HCl-catalyzed sol-gel reactions of tetraethyl orthosilicate (TEOS) and styrene-maleic anhydride copolymer in the presence of 3-aminopropyl triethoxysilane (APTES) as a coupling agent and citric acid as a nonsurfactant template or pore-forming agent, followed by ethanol extraction. Characterization results from nitrogen sorption isotherms and powder X-ray diffraction indicate that polymer-modified mesoporous materials with large specific surface areas (e.g. 900 m(2)/g) and pore volumes (e.g. 0.6 cm(3)/g) could be prepared. As the citric acid concentration is increased, the specific surface areas, pore volumes and pore diameters of the hybrid materials increase.

CONTROLLED RADICAL COPOLYMERIZATION OF STYRENE AND MALEIC ANHYDRIDE UNDER GAMMA RADIATION IN THE PRESENCE OF BENZYL DITHIOBENZOATE

The copolymerization of styrene (St) with maleic anhydride (MAh) under gamma radiation at room temperature in the presence of benzyl dithiobenzoate (BDTB) was found to display 'living' nature evidenced by constant concentration of chain radicals during the copolymerization, linear evolution of molecular weights with conversion and narrow molecular weight distribution (M-w/M-n = 1.23-1.35). The compositional analysis and the sequence structural information of the copolymers obtained from DEPT (Distortionless Enhancement by Polarization Transfer) experiments demonstrate that the copolymers obtained also possess strictly alternating structure.

PHOTOCOPOLYMERIZATION OF MALEIC ANHYDRIDE AND VINYL ACETATE IN TETRAHYDROFURAN~*

The copolymerization of maleic anhydride and vinyl acetate in tetrahydrofuran was studied. Results show that the maximum copolymerization rate is in 0.6 mole fraction of maleic anhydride, indicating the involvement of maleic anhydride-tetrahydrofuran charge transfer complex in the chain initiation process. ESR study provides collateral evidence for the formation of maleic anhydride radical and tetrahydrofuran radical.

Safety evaluation of long-term vas occlusion with styrene maleic anhydride and its non-invasive reversal on accessory reproductive organs in langurs

Aim:To evaluate the safety of the long term vas occlusion with styrene maleic anhydride (SMA) and its non-invasive reversal at the level of accessory reproductive glands (ARGs) in langurs.Methods:The morphology of seminal vesicle and ventral prostate was evaluated by light as well as transmission electron microscopy.Serum clinical chemistry and urine albumin were evaluated in an autoanalyzer using reagent kits.Fructose,acid phosphatase and zinc in the seminal plasma were evaluated spectrophotometrically according to the WHO manual.Serum testosterone, prostate specific antigen and sperm antibodies were evaluated by enzyme-linked immunosorbent assays (ELISA) using reagent kits and hematology was estimated according to standard procedures.Results:The morphological features and secretory activity of the seminal vesicle and prostate were normal as evidenced by the presence of well- developed mitochondria,rough endoplasmic reticulum,Golgi bodies,secretory granules and normal nuclear charac- teristics throughout the course of investigation.Serum testosterone and prostate specific antigen remained unaltered and serum antisperm antibodies level presented negative titres.Urine albumin was nil.Total red blood corpuscles (RBC),white blood corpuscles (WBC),hemoglobin (Hb) and red cell indices,serum protein,glucose,cholesterol, creatinine,creatine kinase (CK),serum glutamate oxalate transaminase (SGOT),serum glutamate pyruvate transami- nase (SGPT),lactate dehydrogenase (LDH),bilirubin,urea,triglycerides and high-density lipoprotein (HDL) did not show appreciable changes following vas occlusion and after its non-invasive reversal.Although fructose,acid phos- phatase (ACP) and zinc in the seminal plasma showed a significant reduction following vas occlusion,it could not be related to the morphology of seminal vesicle and prostate.Conclusion:SMA vas occlusion and its non-invasive reversal do not damage the accessory reproductive organs.

GRAFTING OF PEROXIDE-INITIATED MALEIC ANHYDRIDE ON SPHERICAL PE/PPIN-REACTOR BLEND GRANULES

Spherical polyethylene/polypropylene (PE/PP) in-reactor blend granules with various ethylene/propylene molar ratios and high porosity were synthesized using a high yield TiCVMgCl2 supported catalyst. A solution of benzoyl peroxide (BPO)/maleic anhydride (MAH)/xylene (interfacial reagent) or BPO/MAH/St (comonomer) was absorbed onto the PE/PP in- reactor blend granules, and solid phase graft polymerization of MAH on PE/PP was conducted. The amount of grafted MAH on PE/PP was measured through chemical titration. The results showed that solid phase graft polymerization of MAH in PE/PP in-reactor blend granules produced graft copolymer with high amount of grafted MAH, and the amount of grafted MAH was raised slightly when St was introduced as comonomer. The graft in-reactor blend was fractionated into five fractions through temperature-gradient extraction fractionation (TGEF), and the fractions were analyzed by FTIR. The results revealed that MAH is mainly grafted on the PE segments, whereas MAH was predominantly grafted on the PP segments when St was present in the graft polymerization system. In addition, the final product is still in the form of regular spherical granules, which is beneficial for industrial processing.

Selective Hydrogenation of Maleic Anhydride to Succinic Anhydride over Nickel Catalyst Supported on Carbon Microspheres

The colloidal carbon microspheres(CMS)were prepared by the hydrothermal method.The nickel catalysts supported on carbon microspheres(Ni/CMS)were further prepared and were characterized by the Fourier transform infrared spectroscopy(FTIR),the X-ray diffraction(XRD),the scanning electron microscopy(SEM),the transmission electron microscopy(TEM),and the N_(2)adsorption technique.The selective hydrogenation of maleic anhydride(MA)to succinic anhydride(SA)over the Ni/CMS catalysts was investigated.The results indicated that the Ni/CMS catalyst,which was prepared with glucose as carbon source and calcined at 500℃,exhibited the best performance.The hydrogen pressure,reaction temperature,and reaction time could significantly affect the conversion of maleic anhydride during the hydrogenation reaction.A 98.4%conversion of MA and an 100%selectivity to SA were achieved over the Ni/CMS catalyst in acetic anhydride solvent under mild conditions covering a temperature of 90℃,a H2 pressure of 1.0 MPa,and a reaction time of 3 h.

The UV Aging Properties of Maleic Anhydride Esterified Starch/Polylactic Acid Composites

Esterified starch/polylactic acid（ES/PLA） blending composite was prepared by melting extrusion with maleic anhydride esterified starch and PLA as the raw materials. The composite was accelerated aging by using UV aging box, and its properties were characterized by Fourier transform infrared spectroscopy（FT-IR）, scanning electron microscopy（SEM）, X-ray diffraction（XRD）, thermo gravimetric analysis（TGA） and mechanical testing machine. FT-IR and SEM results show that the infrared absorption peak intensities of C-O, C-H, and C=O in aged samples decrease gradually with increasing aging time. The damage degree of surface and internal of aged samples increases gradually. XRD analysis results show that after aging treatment, the crystalline diffraction peak of thermoplastic esterified starch at 2θ = 21° disappears and the diffraction peaks of PLA at 2θ = 16.5° appear, indicating that the hydrolysis rate of esterified starch is greater than that of PLA. The crystallinity of PLA in aged sample shows an increasing trend at first followed by a decreasing one along with the increasing time of aging treatment, suggesting that the hydrolysis of amorphous regions of PLA is more preferential than its crystalline regions. Because of the influence of crystal structure and the change of composition structure, the initial decomposition temperature of aging test specimen gradually increases with the extension of aging time. The maximum decomposition rate temperature and residual mass increases at first, and then decrease after the aging time extending to 1600 h. As the aging time increases, the damage degree of combination interface between esterification starch and PLA is exacerbated, resulting in the tensile strength and bending strength of aged specimen decreasing gradually.

Surface Modification of Waste Tire by Grafting with Styrene and Maleic Anhydride

Waste tire powder, as waste rubber WR was subjected to grafting with styrene (St) and maleic anhydride (MA). Hydrogen peroxide H2O2 was used to initiate the free radical copolymerization of St onto WR. A thermal initiation was used in case of grafting of MA onto WR. Effect of initiator and monomer concentrations together with the influence of reaction temperature and reaction time were investigated. The grafting was estimated by weight, and the grafted copolymers were characterized by FT/IR, DSC and SEM to prove the grafting. It has found that the grafting increases with increase monomer and initiator concentrations. The increase in the reaction temperature and time also causes increasing levels of the grafted St and MA.

Effect of Residual Maleic Anhydride in PP-g-MAH on the Thermo-Oxidative Aging Properties of RGF-PP

The mechanical, morphological and thermo-oxidative aging properties of the glass fiber reinforced polypropylene (RGF-PP) were studied based on four different maleic anhydride grafted polypropylene (PP-g-MAH) compatibilizers with different content of residual maleic anhydride (MAH). It was shown that PP-g-MAH compatibilizer could significantly improve the mechanical properties of RGF-PP, while from thermal and morphological analysis results, the content of residual MAH had negative influence on long term thermo- oxidative aging properties of RGF-PP with adding PP-g-MAH compatibilizer;the lower the residual content of MAH is, the better the thermo stability of the PP-g-MAH is, and also the better the thermo-oxidative aging properties was obtained.

Promotional Effect of CoO(OH) on Selective Hydrogenation of Maleic Anhydride to γ-Butyrolactone over Supported Ruthenium Catalyst

A decorated ruthenium catalyst was prepared by the coprecipitation method and used for the selective hydrogenation of maleic anhydride(MA) to γ-butyrolactone(GBL). The as-prepared catalyst was characterized by XRD, TGDTG and N2 adsorption techniques. The characterization tests revealed that the catalyst carrier was composed of monoclinic zirconia(m-ZrO2) and hydroxyl cobalt oxide(CoO(OH)). The hydrogenation results showed that the content of CoO(OH), the reaction temperature, the hydrogen pressure and the reaction time significantly affected the catalytic selectivity to GBL. The promotional effect of CoO(OH) was remarkable, which led to an obvious increase in GBL selectivity. An 100% MA conversion and 92.0% selectivity to GBL were achieved over the Ru/ZrO2-CoO(OH)(35%) catalyst in water solvent under the conditions involving a reaction temperature of 180 ℃, a hydrogen pressure of 3.0 MPa, and a reaction time of 6 h.

Properties of Esterified Wood Prepared with Maleic Anhydride/Tetrabr Omophthalic Anhydride/Glycerol Mixture

For overcoming disadvantages of wood, an esterification process was employed and tetrabromophthalic anhydride (TBPA) was used as a reactive chemical agent to prepare an esterified wood with the high dimensional stability, flame resistance, and resistance to biodegradation from water-leaching. The experimental results indicated that esterification of wood plus maleic anhydride / tetrabromophthalic anhydride / glycerol could endow wood with dimensional stability, the antiswelling efficiency during water absorption (ASEw), reduction in water absorptivity (RWA), antiswelling efficiency during moisture absorption (ASEm), moisture excluding efficiency (MEE), and oxygen index (OI) of treated wood increased with an increase in the weight percent gain (WPG). And the treated wood showed great decay resistance and resistance to water leaching, too.

PHOTOCOPOLYMERIZATION OF MALEIC ANHYDRIDE AND VINYL ACETATE

The charge-transfer complex of maleic anhydride and vinyl acetate was copolymerized under UV light. The chain composition and structure of the copolymer were analyzed with conductometry and NMR, and the chain sequence was determined as alternating. The copolymerization rates at different feed ratios, temperatures and in different solvents were investigated, giving evidence to the very active involvement of the CT complexes in the copolymerization. Terpolymerization with acrylonitrile also showed that the complex mechanism was a proper one for this system.

Solvent-free esterification of poly(vinyl alcohol) and maleic anhydride through mechanochemical reaction

A solid-state mechanochemical processing, that is, pan-milling, was used to conduct the esterification of poly（vinyl alcohol） （PVA） with maleic anhydride （MA） through stress-induced reaction. FTIR spectrum study indicated the presence of ester linkages and olefinic double bonds in maleic anhydride cross-linked PVA. Thermal properties of the cross-linked product were characterized by DSC. The results showed its glass transition temperature was 20 ℃ higher than the original linear PVA and the thermal stability was also improved.