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.

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.

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.

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.

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.

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.

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.

Investigation of Plasma Polymerized Maleic Anhydride Film in a Middle Frequency Dielectric Barrier Discharge

Plasma polymerized maleic anhydride （MA） was carried out by using maleic anhydride supersaturated ethanol solution as a precursor in a dielectric barrier discharge （DBD）. The film properties were characterized by water contact angle （WCA）, Fourier transfer infrared （FTIR）, X-ray photoelectron spectroscopy （XPS）, atomic force microscope （AFM） analysis, and a thickness profilometer. The influence of the processing parameters on the film properties such as tile power frequency and polymerization zone was investigated. The results show that anhydride group incorporated into the growing films is favorable at the frequency of 80 kHz and working pressure of 50 Pa. The poly （maleic anhydride） film is uniform and compact at an average deposition rate of 8 nm/min.

Grafting Maleic Anhydride onto Carbon Fiber via a Solid-phase Grafting Method

By combining the strong and light carbon fibers （CFs） with polymers, composite materials with extraordinary mechanical properties are achieved. However, the mechanical properties of the as-prepared CF-reinforced polymer composites can not satisfy the applications in certain fields, especially for the poor interactions between CFs and the polymers. To enhance the mechanical properties of composite materials, a solid phase grafting method has been developed to improve the adhesion forces between CFs and the polymer, by modifying the surfaces of CFs. The effects of the reaction temperature, reaction time, as well as the dosage of the initiator and maleic anhydride （MAH） on the grafting efficiency have been investigated systematically. The structure and the surface chemistry of functionalized CFs have been characterized by Fourier Transform Infrared （FT-IR）, Scanning Electron Microscope （SEM）, X-ray Photoelectron Spectroscopy （XPS）, Thermogravimetric （TG）, and contact angle test. All of these results demonstrate that MAH is grafted onto the surface of CFs successfully by the solid phase grafting method. The MAH grafted CFs significantly improve its wettability, which further improves the interfacial adhesion between CFs and the polymeric matrix. The optimal reaction conditions are determined, such as the MAH/CF molar ratio, the dosage of initiator, the reaction temperature and the reaction time to be 3/1, 2%, 90℃ and 4 h, respectively. These attractive interracial characteristics of modified CFs suggest that the method proposed herein is a novel and efficient approach to develop CF-reinforced polymer composites with outstanding mechanical properties for cutting-edge industrial applications.

CHARGE-TRANSFER AND ENERGY-TRANSFER IN THE PHOTO-INDUCED COPOLYMERIZATION OF 2-VINYLNAPHTHALENE WITH MALEIC ANHYDRIDE

The initiation mechanism of the copolymerization of 2-vinylnaphthalene with maleic anhydride was studied under irradiation of 365 nm. The excited complex was formed from (1) the local excitation of 2-vinylnaphthalene followed by the charge-transfer interaction with maleic anhydride and (2) the excitation of the ground state charge-transfer complex, and then it collapsed to 1,4-tetramethylene biradical for initiation. A1: 1 alternating copolymer was formed in different monomer feeds. Addition of benzophenone could greatly enhance the rate of copolymerization through energy-transfer mechanism.

Synthesis and Characterization of Styrene-Maleic Anhydride-Butyl Acrylate Terpolymer

A novel surface modifying agent and internal compatilizer of inorganic and macromolecule composite materials,P(St/MAH/BA)terpolymer,was synthesized in butanone by solution polymerization method using styrene(St),maleic anhydride(MAH),and butyl acrylate(BA)as monomers and azobisisobutyronitrile(AIBN)as an initiator.Some affecting factors on terpolymers yields such as polymerization time,reaction temperature,solvent volume,initiator content,and reactants ratios were studied.Furthermore,the structure and thermal properties of terpolymers were primarily characterized and determined by Fourier Transform Infrared Spectroscopy(FTIR),nuclear magnetic resonance(NMR),thermogravimetric analysis(TGA),and gel permeation chromatography(GPC).The results indicate that the terpolymers are random polymers and the yields are low,but the thermal decomposed temperature of terpolymers P(St/MAH/BA)is around 220 ℃ and the average molecular weights(Mw)achieve 1.189×105 g·mol-1.

A Proposed Stereochemical Mechanism for the Improved Preparation of Maleic Anhydride Cycloadduct of CLA

The fatty acid derivatives, prepared from renewable natural oils, can be used as highly promising and potential substitutes for petrochemicals. The study of process improvement and stereochemical mechanism for preparing these derivatives would be beneficial for their industrial production. Conjugated linoleic acid (CLA) containing 9cis-11trans (9c, 11t) and 10trans-12cis (10t, 12c) isomers was prepared from Salicornia herbacea seed oil. Maleic anhydride cycloadduct of CLA (MAC) was prepared by an improved process, and it was characterized by FTIR, 1H and 13C NMR, etc. A new method to calculate conformers-ratio of CLA or MAC was also developed. Furthermore, the stereochemical mechanism for the improved preparation of MAC was proposed primarily by the calculation method above. The following observations were made: 1) The yield of MAC could reach as high as 96.7% under mild reaction conditions and with an easy and efficient product separation;2) The trans-trans CLA in the s-cis conformation acted as a predominant reactant to Diels-Alder [4 + 2] cycloaddition of maleic anhydride, which was the main reaction occurred simultaneously with catalytic configurational isomerizations of CLA in one step;3) From all studied CLA conformers, the most stable conformation was the s-trans conformation of trans-trans CLA, while the s-cis conformation of trans-trans CLA had the most favorable structural parameters for cyclohexenyl ring formation;4) Four MAC conformers derived from 9c, 11t- and 10t, 12c-CLA, were obtained as final main products that were determined to be cis-cycloadducts;5) The endo/exo ratios of the cis- cycloadducts derived from 9c, 11t- and 10t, 12c-CLA, were 2.14:1 and 1.99:1, respectively;and 6) The results obtained from the calculation method above were in excellent accordance with those from our experiments.

Development of a correlation equation between the diesterification of maleic anhydride and the acidic ionic liquids nature

The sustainable synthesis of dimethyl maleate via diesterification through the utilization of ionic liquid(IL)is of great importance.However,the relationship between the ILs nature and the reactivity of diesterification is still unclear.Herein,a series of ILs with different structures were selected for the comprehensive investigation of diesterification.The acidity(H_(0))and Kamlet-Taft solvent parameters(hydrogen bond donor ability(α),hydrogen bond acceptor ability(β),and polarizability(π^(*)))of ILs were measured by UV–Visible spectroscopy,and the effects of them on the diesterification of maleic anhydride were also studied in detail.The results indicated that not only H0of the IL-based catalysis system,but also itsα,β,andπ^(*)influenced the reaction activity of diesterification.Furthermore,a quantifiable correlation was fitted between the natural logarithm of the rate constant and multiple parameters of ILs,indicating that the diesterification rate had a positive correlation with the H0,α,andπ^(*),and inverse correlation with theβof the IL.A plausible synergetic reaction mechanism for the excellent performance of[(HSO_(3))PMim][HSO_(4)]has been proposed.Overall,this work thoroughly explored the relationship between the nature of ILs on diesterification in-depth,which will reveal the nature of diesterification in detail.