Ionic liquid-assisted preparation of hydroxyapatite and its catalytic performance for decarboxylation of itaconic acid

The synthesis of methacrylic acid from biomass-derived itaconic acid is a green route,for it can get rid of the dependence on fossil resource.In order to solve the problems on this route such as use of a preciousmetal catalyst and a corrosive homogeneous alkali,we prepared a series of hydroxyapatite catalysts by an ionic liquid-assisted hydrothermal method and evaluated their catalytic performance.The results showed that the ionic liquid[Bmim]BF_(4) can affect the crystal growth of hydroxyapatite,provide fluoride ion for fluorination of hydroxyapatite,and adjust the surface acidity and basicity,morphology,textural properties,crystallinity,and composition of hydroxyapatite.The[Bmim]BF4 dosage and hydrothermal temperature can affect the fluoride ion concentration in the hydrothermal system,thus changing the degree of fluoridation of hydroxyapatite.High fluoride-ion concentration can lead to the formation of CaF_(2) and thus significantly decrease the catalytic performance of hydroxyapatite.The hydrothermal time mainly affects the growth of hydroxyapatite crystals on the c axis,leading to different catalytic performance.The suitable conditions for the preparation of this fluoridized hydroxyapatite are as follows:a mass ratio of[Bmim]BF4 to calcium salt=0.2:1,a hydrothermal time of 12 h,and a hydrothermal temperature of 130℃.A maximal methacrylic acid yield of 54.7%was obtained using the fluoridized hydroxyapatite under relatively mild reaction conditions(250℃ and 2 MPa of N_(2))in the absence of a precious-metal catalyst and a corrosive homogeneous alkali.

Influence of Ca/P ratio on the catalytic performance of hydroxyapatite for decarboxylation of itaconic acid to methacrylic acid

Methacrylic acid,an important organic chemical,is commercially manufactured starting from fossil feedstock.The decarboxylation of itaconic acid derived for biomass is a green route to the synthesis of methacrylic acid.In view of the problems existing in the researches on this route such as use of noble metal catalyst,harsh reaction conditions and low desired-product yield,we prepared a series of hydroxyapatite catalysts with different Ca/P molar ratios and evaluated their catalytic performance.The results showed that the hydroxyapatite catalyst with a Ca/P molar ratio of 1.58 had the best catalytic activity.The highest yield of MAA up to 61.2%was achieved with basically complete conversion of itaconic acid under the suitable reaction conditions of 1 equivalent of NaOH,2 MPa of N_(2),250℃,and 2 h.On this basis,a reaction network for the decarboxylation of itaconic acid to methacrylic acid catalyzed by hydroxyapatite was established.With the aid of catalyst characterization using X-ray powder diffraction,NH3/CO2 temperature-programmed desorption,N_(2)physisorption,inductively coupled plasma optical emission spectrometry,and scanning electron microscopy,we found that the distribution of surface acid sites and basic sites,crystal growth orientation,texture properties and morphology of hydroxyapatite varied with the Ca/P molar ratio.Furthermore,the change of the crystal growth orientation and its influence on the surface acidity and alkalinity were clarified.

CONFORMATIONAL CHARACTERISTICS OF POLY(ACRYLIC ACID) AND POLY(METHACRYLIC ACID)

A full-relaxation optimization of molecule and the Dreiding force field are employed to obtain the geometry parameters and the conformational energy surfaces of meso or racemic dyad of poly(acrylic acid) (PAA) and poly(methacrylic acid) (PMAA). Three different carbonyl-bond orientations of side-groups resulted in the differences in depth of potential wells in their energetic contours for a meso or a racemic dyad. These discrepancies are interpreted as a result of various fine structures corresponding to grid search conformations as well as thereby different interactions. The analysis on the most stable conformations of PMAA confirmed that the ester groups are nearly perpendicular to the plane defined by the two adjacent skeletal bonds but may possibly change their relative orientations to meet the requirement of lower energy during the conformational state transition. For each polymer, two global energy maps of a meso and a racemic dyad were finally constructed from the superposition of energy data for the three kinds of side-group orientations by the Boltzmann factors. From an ensemble average, the proposed scheme with three rotational isomeric states (RIS) allowed us to access the experimentally unperturbed dimensions of PAA chain via the configurational statistical mechanics. Although the calculation was based on the short-range, local interactions, it was interested to note that the experimental characteristic ratios just fell within the range calculated for atactic chains.

Flavonoids and Amino Acids Analysis of the Fruits of Cornus mas L. Introduced in Uzbekistan

Cornelian cherry is used in the food and pharmaceutical industry as an ornament, in traditional medicine, and in the manufacture of household items. It is widely used in medicine for the prevention and treatment of many diseases. Therefore, it is important to research the chemical composition of these species. In the article, based on our research, the analysis of the quantitative calculation of flavonoids and amino acids of the fruits of the “Elegant” and “Svetlyachok” cherry varieties was carried out. It was found that the amount of amino acids in the fruits of Cornus mas L., introduced in Uzbekistan, is higher in the variety “Svetlyachok” 2.643235 mg/g. In “Elegant” variety it was 1.794235 mg/g. The amount of 4 different flavonoids in the fruit was also determined. It has been established that the Elegant variety has a high concentration of lutein and rutin, and the svetlyachok has a high concentration of apigenin and quercetin.

Highly efficient Rod-shape Poly(methacrylic acid-co-styrene-codivinylbenzene)High-performance Liquid Chromatographic Column

A highly efficient copolymer (methacrylic acid - co - styrene - divinylbenzene) in situ making high-performance liquid chromatographic column was prepared and evaluated. The column efficiency calculated in terms of height equivalent to a theoretical plate was 25 mu m and rapid separations of small molecules such as substituted aromatic hydrocarbons and aromatic acids were achieved within five minutes.

The Effect of Methacrylic Acid and Maleic Acid on the Isothermal Kinetics of Acrylic Acid Crosslinking Co-polymerization under Conventional and Microwave heating

The kinetics of free-radical crosslinking co-polymerization(FRCCP)of acrylic acid(AA)with both methacrylic acid(MA)(PAMA hydrogel)and maleic acid(MAL)(PAMAL hydrogel)was investigated under the conditions of isothermal conventional heating(CH)and under the conditions of microwave heating(MWH)with controlled cooling.The kinetics curves of FRCCP of PAMA and PAMAL hydrogels under the conditions of CH are described with the kinetics model of second order chemical reaction,whereas the kinetics curves under the conditions of CH are described with the kinetics model of Polany-Winger.It is proved that MWH leads to the changes in the rate of FRCCP and to the changes in the values of the kinetic parameters activation energy(Ea)and pre-exponential factor(lnA).It was found the existence of relationship between the values of the kinetic parameters calculated for MWH and CH for PAMA and PAMAL hydrogel synthesis process,which is well-known as compensation effect.The effect of MWH on the kinetics of FRCCP for PAMA and PAMAL hydrogel formation were explained by applying the model of activation by selective energy transfer(SET).The changes in kinetics model,rate of FRCCP and kinetics parameters,caused with the MWH can found wide application in designing novel technologies for obtaining polymers and for synthesis of polymers with novel physico-chemical properties.The suggested mechanism of activation for polymerisation under the conditions of MWH also enables development of novel reaction systems and technologies for polymers productions.

羧基功能化微滤膜PSF-g-PMAA的制备及对三嗪类除草剂的截留去除性能

使用过硫酸盐在胺基化的氯甲基化聚砜微滤膜表面形成—NH2/S2O82-氧化还原引发体系,将甲基丙烯酸(MAA)接枝聚合到聚砜微滤膜表面,得到羧基功能化PSF-g-PMAA微滤膜.采用等温吸附和渗透实验,考察了PSF-g-PMAA膜对三嗪类除草剂(扑草净、莠灭净、阿特拉津)的截留去除性能.结果表明,基于静电相互作用和氢键的协同吸附作用,PSF-g-PMAA膜对三嗪类除草剂显示出良好的去除效果,其中对莠灭津的最大吸附量达到0.18μmol/cm^(2)(41μg/cm^(2)).采用膜面积为1.77 cm^(2)的注射过滤器,PSF-g-PMAA膜对浓度为0.8 mg/L的三嗪类除草剂溶液的截留率接近100%(渗透液体积100 mL).

交联PMMA@玻尿酸微胶囊的制备及其释放性能

为成功制备玻尿酸微胶囊,在水/油(W/O)反相乳液体系中通过自由基聚合制备了以玻尿酸水溶液为芯材、季戊四醇四丙烯酸酯(PET4A)交联甲基丙烯酸甲酯(MMA)聚合物为壁材的微胶囊。采用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、傅里叶红外光谱仪(FTIR)、激光散射粒度分布分析仪(LSPSDA)、紫外分光光度计(UV)对微胶囊的形貌、结构、粒径分布、包覆率及释放性能进行了表征。结果表明:微胶囊具有不规则球形及核壳结构形貌。当油水比为10∶1、芯壁比为1∶1、玻尿酸用量为1.5 mg/mL、交联剂添加量为0.67%(相对于壁材)时,微胶囊包覆率与载药率分别达到极大值81.40%和1.221%,表面形貌最好,其粒径在1.4~2.0μm之间。微胶囊累计释放量随交联剂用量的升高而下降,同时微胶囊具有pH响应性,pH=5.5时累计释放量最大。

Characterization and Thermal Conductivity of Modified Graphite/Fatty Acid Eutectic/PMMA Form-Stable Phase Change Material

We prepared and characterized a form-stable composite phase change material （PCM） with higher thermal conductivity. Capric acid（CA）-myristic acid（MA） eutectic as core, poly-methyl methacrylate （PMMA） as supportive matrix and modified graphite （MG） powders serving as the thermal conductance improver were blended by bulk- polymerization method. The composite PCMs with different MG mass fraction （2%, 5%, 7%, 10% and 15%） were characterized by FT-IR, SEM, DSC technique and mechanical tests. Thermal conductivities of the composites were measured by transient hot-wire method. The results indicate that MG powders have been successfully inserted into the CA-MA/PMMA matrix without any chemical reaction with each other. The MG/CA-MA/PMMA composites maintain good thermal storage performance while the thermal conductivity has been enhanced significantly. The composite PCM added with 15 wt% MG powders increases approximately as 195.9% in thermal conductivity. Moreover, the thermal conductivity improvement of the composite PCMs is also verified by the melting-freezing experiment, which is profitable for the heat transfer efficiency in latent heat thermal energy storage system.

Process design and economic analysis of methacrylic acid extraction for three organic solvents

In this work,a techno-economic study for the solvent based extraction of methacrylic acid from an aqueous solution is presented.The involved phase equilibrium calculations in process design are verified by measured experimental data.First,experiments are conducted with different solvent candidates to measure LLE(liquid–liquid equilibrium)data and to establish the effects of extraction temperature and dosage of solvent.Next,the binary interaction parameters for the UNIQUAC model to be used for equilibrium calculations are fine-tuned with measured data.Then,a process for the solvent based extraction of methacrylic acid recovery is designed and verified through simulation with the regressed UNIQUAC model parameters.The optimal configuration of the process flowsheet is determined by minimizing the total annualized cost.Among the three solvent candidates considered-cyclohexane,hexane and toluene-the highest efficiency and the lowest total annualized cost is found with toluene as the solvent.

Synthesis,Characterization and Catalytic Application of H_3PW_(12)O_(40)/MCM-48 in the Esterification of Methacrylic Acid with n-butyl Alcohol

A novel environmental friendly catalyst, H3PW12O40/MCM-48, was prepared by impregnation method. The catalysts were characterized by means of XRD and FT-IR. The synthesis of n-butyl methacrylate catalyzed by H3PW12O40/MCM-48 was studied with methacrylic acid and n-butyl alcohol as reactants. H3PW12O40/MCM-48 is an excellent catalyst for synthesizing n-butyl methacrylate and Keggin structure of H3PW12O40 kept unchanged after being impregnated on surface of the molecular sieve support. Effects of n（methacrylic acid）：n（n-butyl alcohol）, catalyst dosage, cyclohexane（water-stripped reagent） and reaction time on yields of the product were investigated. The optimum conditions have been found, that is, molar ratio of acid to alcohol is 1：1.6, mass ratio of catalyst used to the reactants is 0.5% and reaction time is 2.0 h. Under these conditions, the yield of n-butyl methacrylate can reach 93.7%.

PLA-g-GMA的制备及其对PBAT/PLA共混物结晶性能的影响

以制备的聚乳酸(PLA)-甲基丙烯酸缩水甘油酯(GMA)接枝物(PLA-g-GMA)为聚(对苯二甲酸/己二酸丁二酯)(PBAT)与PLA共混物的相容剂,制得了PBAT/PLA共混物。采用FTIR、^(1)HNMR分析了GMA质量分数对PLA-g-GMA接枝率的影响。发现当GMA质量分数为20%时,制备的PLA-g-GMA(G-20)有效接枝率为6.44%。通过DSC、SEM考察了G-20质量分数对PBAT/PLA共混物(BAx,其中,x%为G-20的质量分数,下同)结晶以及微观形貌的影响。结果表明,G-20的加入使共混物中PLA在降温过程中形成的结晶结构更完善,BA6冷结晶峰消失;BA4结晶温度由未添加相容剂共混物(BA0)的75.4℃降至68.0℃;G-20的加入使共混物在结晶初期速率常数由0.83(BA0)降至BA10的0.68,抑制了初期PLA晶核产生,但促使第2阶段结晶速率由1.28(BA0)提高到1.38(BA2),促进了PBAT晶体生长;G-20使脆断截面中PLA与PBAT之间剥离程度减小;BA8纤维强度由BA0的0.25 cN/dtex提高至0.33 cN/dtex。

Nitroxide-Mediated Photo-Controlled/Living Radical Polymerization of Methacrylic Acid

The photo-controlled/living radical polymerization of methacrylic acid (MAA) was performed at room temperature by irradiation with a high-pressure mercury lamp using azo initiators and 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl as the mediator in the presence of (4-tert-butylphenyl)diphenylsulfonium triflate (tBuS) as the accelerator. Whereas the bulk polymerization yielded polymers with a bimodal molecular weight distribution in both the absence and presence of tBuS, the solution polymerization in methanol produced unimodal polymers with the molecular weight distribution of 2.0 - 2.3 in the presence of tBuS. The molecular weight distribution of the resulting poly (MAA) decreased with an in- crease in tBuS. The dilution of the monomer concentration also reduced the molecular weight distribution. The use of the initiator with a low 10-h half-life temperature also effectively controlled the molecular weight. The livingness of the polymerization was confirmed by obtaining linear increases in the first-order conversion versus time, the molecular weight versus the conversion, and the molecular weight versus the reciprocal of the initiator concentration.

Preparation,Characterization and Service Performance of Fatty Acid/PMMA Shape-Stabilized Phase Change Material

A series of fatty acid/poly methyl methacrylate(PMMA) shape-stabilized phase change materials(PCMs) have been prepared by bulk polymerization method.In the composite,fatty acid(capric acid,stearic acid,and their eutectic mixture) acts as core material and PMMA serves as matrix,which coats the fatty acid to prevent the leakage of melted fatty acid.The prepared shape-stabilized PCMs were characterized on the morphology,phase change behavior,chemical characterization and thermal properties.The results indicate that the composites with proper phase change temperature and latent heat are able to keep solid morphology in macro level during thermal storage process.Thermal cycling test also indicates that the composite PCMs have good thermal reliability.Moreover,thermal conductivity and thermal performance are investigated and the results show that the shape-stabilized PCMs have the higher thermal conductivity than fatty acid and exhibited good thermal performance in controlling the atmosphere temperature.

PROPERTIES AND SYNTHESIS OF NEW SUPPORTS FOR IMMOBILIZATION OF ENZYMES BY COPOLYMERIZATION OF VINYLENE CARBONATE AND METHACRYLIC ACID

Methacrylic acid first was neutralized with an aqueous solution of NaOH to pH = 6.0 similar to 7.0, vinylene carbonate (VCA) was added to the solution, then monomers were copolymerized in paraffin oil by means of reverse-phase suspension polymerization and hydrophilic copolymeric supports were prepared. The properties of the supports were determined using trypsin and results show that the amount of enzymes coupled to the supports and the specific activity of immobilized trypsin are related to the content of VCA structure units, reaction time and concentration of enzyme solution, etc.

Investigation of the Reaction Mechanism of Itaconic Acid/Maleic Acid Copolymer System and Cotton Cellulose

The reaction mechanism of IA/MA copolymer system andcotton cellulose is conjectured and verified, the two keysteps, such as the formation of cyclic anhydride interme-diates and the building of ester crosslinklng, and the ef-fect of sodium hypophosphite are especially emphasized,by FT - IR spectroscopy and acid- base titration anal-yses. The experiments reveal that carboxylic acids main.ly change to cyclic anhydride in the pre - drying step andSodium Hypophosphite (SHP) has effect on it, but mostester - crosslinkages are built in the curing step and SHPhas effects on both anhydride formation and ester -crosslinking formation.

INFLUENCES OF ACID POST-TREATMENT ON THE MORPHOLOGY OF SOAP-FREE P(MMA-EA-MAA)PARTICLES PREPARED BY SEEDED EMULSION POLYMERIZATION

Soap-free poly（methyl methacrylate-ethyl acrylate-methacrylic acid） latex particles with narrow size distribution were synthesized by seeded emulsion polymerization, and the porous particles were created by a stepwise alkali/acid treatment method. Effects of acid treatment conditions on the particle morphology were investigated. Results show that one to three pores were formed inside most of particles after post-treatment. At pH 7.0, when the treatment temperature was lower than 70℃, the size of particles and the volume of pores remained almost unchanged, and these two values increased significantly when the temperature was higher than 70℃. Both the particle size and the pore volume decreased with the increase of initial pH value and treatment time in the acid treatment. As the pH was below 4.0 and the treatment time was longer than 180 min, the particles shrunk in size.

A NEW METHOD FOR THE SYNTHESIS OF METHACRYLIC ACID FROM ISOBUTYRALDEHYDE

Isobutyraldehyde was used as starting material via three steps: oxidation, chlorination and dehydro-chlorination to yield methacrylic acid. The total yield of methacrylic acid is 49.7%.

MMA-co-GMA增容PBAT/PLA共混材料结构与性能

利用甲基丙烯酸甲酯-甲基丙烯酸缩水甘油酯无规共聚物(MG)为相容剂,采用熔融共混法制备了聚对苯二甲酸-己二酸丁二醇酯(PBAT)和聚乳酸(PLA)生物降解共混材料。MG中的环氧官能团与PBAT和PLA中的端基之间的增容反应生成PBAT-co-MG-co-PLA大分子相容剂提高二者之间的相容性。MG的加入导致PLA相的最大分解速率温度明显向高温方向移动,耐热性提高,而PBAT相最大分解速率温度几乎没有变化。MG的增容作用促进了PBAT相的均匀分散、较小的粒子尺寸和窄的分布。动态流变测试结果表明,PBAT/PLA/MG共混材料比PBAT/PLA共混物具有更高的复数黏度和储能模量,增容反应增加了界面相互作用和熔体强度。同PBAT/PLA共混材料相比,MG的增容作导致PBAT/PLA/MG共混物表现出更高的冲击韧性、断裂伸长率和拉伸强度。