Surface Modification of Nanoclays with Styrene-Maleic Anhydride Copolymers

This study presents the modification of surfaces of nanoclays, halloysite nanotubes (HNT) and sepiolite (SEP), with styrene-maleic anhydride copolymers (SMA) via esterification reaction between hydroxyl groups of the nanoclays and anhydride groups of SMA. The structural, thermal, and morphological analyses of the modified nanoclays were performed by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction analysis (XRD), thermal gravimetric analysis (TGA), and field emission scanning electron microscopy (FESEM). All of these results suggested that the expected modification of HNT and SEP surfaces were performed. Although XRD patterns of HNT containing samples showed that the basal spacing shifted to higher distances, it was found that those of the crystalline structure of SEP remained unchanged. Thermal gravimetric analysis exhibited that SMA copolymers were grafted onto the surfaces of nanoclays varying amounts between 15 and 43 wt. % depending on the types of nanoclays and SMA copolymers. This modification indicates that these nanoclays can be added to the polystyrene matrix without any compatibilizers.

Influences of Reactive Compatibilizer R-Styrene-Maleic Anhydride Copolymer on PA6/PP Blends

The effect of R-styrene-maleic anhydride copolymer(R-SMA) compatibilzation on Nylon 6(PA6)/polypropylene(PP) blends has been investigated experimentally through Molau test,microscopic morphology,and chemical structure.Results show that the moderate R-SMA addition can promote reaction between anhydride in R-SMA and amino in PA6,and lead to a new PA6-g-R-SMA copolymer in the blends.Such PA6-g-R-SMA copolymer in the blends can effectively reduce the interfacial tension and PP particle size,and improve the compatibility of two immiscible phases in the blends.The crystallinity of PA6 in PA6/PP blends has greatly decreased by PP blends.The blends have the best comprehensive mechanical and thermal properties when the mass ratio of PA6/PP/R-SMA is 90:10:2 to 90:10:4.The impact strength of the PA6/PP blends with the compatibilizer is increased by more than 150%.

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.

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.

Efficient, continuous oxidation of durene to pyromellitic dianhydride mediated by a V-Ti-P ternary catalyst: The remarkable doping effect

Continuous preparation of pyromellitic dianhydride(PMDA) from durene has been studied using a fixedbed reactor. The reaction was performed using a phosphorus-vanadium-titanium ternary catalyst.Relatively high selectivity and yield of PMDA was obtained. The in-situ characterization was combined with theoretical calculation to reveal the reaction mechanisms, and the remarkable doping effect was discussed.

Highly improved cyclic stability of Ni-rich/Li batteries with succinic anhydride as electrolyte additive and underlying mechanism

Lithium-metal battery based on Ni-rich cathode provides high energy density but presents poor cyclic stability due to the unstable electrode/electrolyte interfaces on both cathode and anode.In this work,we report a new strategy to address this issue.It is found that the cyclic stability of Ni-rich/Li battery can be significantly improved by using succinic anhydride(SA) as an electrolyte additive.Specifically,the capacity retention of LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)/Li cell is improved from 14% to 83% after 200cycles at 1 C between 3.0 and 4.35 V by applying 5% SA.The underlying mechanism of SA contribution is understood by comparing the effects of malic anhydride(MA) and citraconic anhydride(CA), both of which share a similar molecular structure to SA but show different effects.On anode side,SA can but MA and CA cannot form a protective solid electrolyte interphase(SEI) on Li anode.On cathode side,three anhydrides can suppress the formation of hydrogen fluoride from electrolyte oxidation decomposition,but SA behaves best.Typically,MA shows adverse effects on the interface stability of Li anode and NCM811 cathode,which originates from its high acidity.Though the acidity of MA can be mitigated by substituting a methyl for one H atom at its C=C bond,the substituent CA cannot compete with SA in cyclic stability improvement of the cell,because the SEI resulting from CA is not as robust as that from SA,which is related to the binding energy of the SEI components.This understanding reveals the importance of the electrolyte acidity on the Ni-rich cathode and the robustness of the SEI on Li anode,which is helpful for rationally designing new electrolyte additives to further improve the cyclic stability of high-energydensity Ni-rich/Li batteries.

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.

RING OPENING COPOLYMERIZATION OF SUCCINIC ANHYDRIDE-ETHYLENE OXIDE BY Al(Ⅲ) ORGANOMETALLIC CATALYSTS

Ring opening copolymerization of succinic anhydride (SA) with ethylene oxide (EO)was successfully carried out by using a series of aluminum-based catalyst in 1,4-dioxane at62±2℃. The results showed that in-situ AlR_3-H_2O (R=ethyl, iso-butyl) catalysts gavehigher molecular weight (M_w～10~4), while Al(OR)_3 catalysts gave the higher alternatingcopolymer structure with slightly lower molecular weight. The in-situ AlR_3-H_2O systemshave been evaluated in more detail for the reaction which showed the optimum H_2O/Almolar ratio to be 0.5. The copolymers with different composition (F_(SA)/F_(EO)= 36/64to 45/55 mol/mol) were synthesized by using different monomer feed ratio. The melt-ing point (T_m), glass transition temperature (T_g) and enthalpy of fusion (ΔH_f) of thesecopolymers are depended on the copolymer composition and in the range of 87～102℃,-12～-18℃, and 37～66J/g, respectively. The second heating scan of DSC also in-dicated that the higher alternating copolymer was more easily recrystallized. The onsetdecomposition temperature was more than 300℃ under nitrogen and influenced by thecopolymer composition.

Au/FeO_x-TiO_2 as an efficient catalyst for the selective hydrogenation of phthalic anhydride to phthalide

Au/FeOx-TiO2,prepared by deposition-precipitation method,is an efficient and stable catalyst for the liquid phase selective hydrogenation of phthalic anhydride to phthalide under mild reaction conditions.

Synthesis of a Poly(amide-imide)from 5,6-Diphenyl-1-chloroformyl3,4-benzenedicarboxylic Anhydride and Bis (4-aminophenyl)ether

A novel poly (amide-imide) was prepared from a novel monomer: 5,6-diphenyl-chloroformyl-3,4-benzenedicarboxylic anhydride and bis (4-aminophenyl) ether. The polymer was characterized by FTIR. (HNMR)-H-1. DSC and TGA.

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.

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.

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.

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.

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.

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.

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.

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.