New biobased carboxylic acid hardeners for epoxy resins

Soybean oil was modified into a novel biobased polyacid hardener by thiol‐ene coupling with thioglycolic acid. The structure of the initial soybean oil and polyacid triglyceride was carefully analyzed using ¹H NMR and titration. The thermal crosslinking reaction between acid hardener and epoxidized resin was studied by differential scanning calorimetry (DSC) and rheology. Then, the synthesized biobased acid hardener was employed as a novel curing agent for bisphenol A diglycidyl ether to elaborate new partially biobased materials. These materials, formulated in stoichiometry ratio, were characterized by DSC, thermogravimetry analyses, dynamic mechanical analyses and exhibit interesting properties for coatings. Practical applications: The products of the chemistry described in this contribution, i.e., polyacid from soybean oil and thioglycolic acid, provide biobased building blocks for further epoxy resin syntheses by reaction with epoxy groups. The obtained epoxy resins are partially biobased and may be applied as binders and coatings.     

Adsorption of acid dyes using polyelectrolyte impregnated mesoporous silica

Cationic polyelectrolyte, PDDA (Poly(diallyldimethylammonium chloride)), was impregnated on mesoporous silica SBA-15 (PDDA/SBA-15) and amorphous conventional silica (PDDA/CS) supports. Acid dye adsorption characteristics, such as adsorption kinetics, adsorption isotherms, maximum adsorption capacity, and breakthrough curves of the prepared PDDA/SBA-15 and PDDA/CS adsorbents, were examined by batch and column adsorption techniques where the Acid Violet 17, Acid Red 44, and Acid Blue 45 were used as target adsorbates. PDDA/SBA-15 adsorbent showed fast adsorption kinetics of less than 10 min and much higher adsorption capacities compared to PDDA/CS due to large pore sizes, ordered cylindrical pore structures, and high amount of impregnated PDDA. Results from batch and column experiments showed that practical use of PDDA/SBA-15 adsorbent for effective removal of acid dyes from aqueous solution would be possible. Polyelectrolyte impregnation method was suggested as a simple method for the development of adsorbent with large pore diameters and efficient adsorption characteristics.     

Kinetic behavior of photo‐polymerization of UV‐curable resins with carboxylic acid and amino groups

Photo‐polymerization behaviors of bisphenol‐A epoxy diacrylate (EPA) and six kinds of EPA‐derived resins containing different amounts of carboxylic acid, urethane, amide, and imide groups were studied by a photo differential scanning calorimetry. The dark polymerization was performed and pseudo‐steady state assumption of growing radicals was made to obtain the kinetic constants for propagation, bimolecular termination, monomolecular termination, and the concentration of growing radicals of different resins as a function of extent of reaction. Compared with EPA, it was found that the rate of polymerization and kinetic constants of the six resins were relatively small because the mobility of reacting species in resins was restricted by carboxylic acid, urethane, amide, and imide groups. Finally, three different photo‐initiators were used to initiate the polymerization, and their kinetic behaviors were compared. The effect of tertiary amine group of photo‐initiator on the rate of polymerization of resins having carboxylic acid group and the initiator efficiency were discussed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

含磷羧酸类环氧树脂固化剂的合成及固化性能研究

以邻苯基苯酚和三氯氧磷为原料,无水三氯化铝为催化剂,首先合成9,10-二氢-9-氧杂菲-10-膦酰氯(ODC)。再以乙酸为溶剂,通过ODC与酒石酸(TA)的反应,合成了新型含磷羧酸类环氧树脂固化剂2,3-二9,110-二氢-9-氧杂菲-10-膦氧基)丁二酸(ODC-TA)。通过红外光谱、H核磁共振谱对ODC和ODC-TA的结构进行了表征,并通过DSC和TGA对ODC-TA/CYD-128型环氧树脂固化体系的固化性能及阻燃性能进行了研究。     

Adsorption of cyanogen chloride on impregnated active carbon

The adsorption of cyanogen chloride on impregnated carbon containing copper and chromium compounds and other additives is accompanied by the formation of carbon dioxide. Presorbed water enhances the formation of carbon dioxide and decreases the desorption of cyanogen chloride. Cyanogen chloride is adsorbed irreversibly because hydrolysis takes place at a rate higher than that of desorption.     

Synthesis of amino acid derivatives of ethanolamine

Summary N-Phthaloylglycylaminocthanol may be prepared in 24% yield by a modification of the Shechan carbodiimide synthesis of peptides of hydroxy amino acids (6). The amino alcohol is characterized as to melting point, solubility in various solvents, the ability to form a derivative with acetic anhydride, percentage of nitrogen, and infrared spectra. In acid solution this compound appears to undergo the aminoacyl shift characteristic of compounds containing an amide linkage and a free hydroxyl group. Attempts to isolated N-glycylaminoethanol by hydrolysis of the phthaloyl derivative with hydrazine hydrate have been unsuccessful. Impure N-phthaloylalanylaminoethanol and N-phthaloylglycylglycylaminoethanol were also synthesized by means of this procedure. Several other methods for synthesizing N-glycylaminoethanol are discussed. Portion of a thesis presented by Elizabeth C. Smith as partial fulfillment of the requirements for the degree of Doctor of Philosophy. Authorized for publication as Paper No. 2399 on Sept. 1, 1959, in the Journal Series of the Pennsylvania Agricultural Experiment Station.     

Preparation and adsorption properties of resins containing amine,sulfonic acid,and carboxylic acid moieties

Completely water‐insoluble resins containing amine, carboxylic acid, and sulfonic acid as ligand groups were synthesized by radical polymerization in solution. The yield was higher than 97%. The resins were characterized by FTIR spectroscopy and thermal analysis. The metal ion retention properties at different pH values were investigated by a batch method. Metal ions studied were: Cu(II), Cd(II), Zn(II), Hg(II), Pb(II), and Cr(III). The metal ion binding ability depended strongly on the pH. The retention properties were also tested under competitive conditions. Elution of the metal ion was investigated in acid medium at different concentrations. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 700–705, 2003     

通过带有裸露羧酸根的Suzuki反应合成联苯羧酸衍生物的研究

Suzuki偶联反应是合成联苯结构的重要方法之一,本文以溴带芳烃和有机硼酸酯为原料,尝试了带有裸露羧酸根的Suzuki反应,并以62%的产率得到了联苯羧酸衍生物。这为联苯衍生物以及含有联苯结构的生物活性分子的快速生产提供了更为多样化的合成路线,为有效地推动联苯结构化合物的工业化生产做出了贡献。     

Synthesis of Imidazoles by reaction of N-benzylated amidines with carboxylic acid derivatives

2-Amino-N-heterocycles, such as 2-aminopyridine 7 or 2-aminobenzimidazole 16 as well as benzamidines 19 possessing a N-(4-nitrobenzyl)-substituent react as N-C-N-C-synthons with formamide chlorides 5 , formamide acetals 2 or acetic anhydride (C₁-building blocks) with formation of imidazole compounds 9 , 17 or 22 , respectively in the presence of triethylamine. In some cases, intermediate N-acetylation ( 20 ) or N-formylation products 21 are isolated.     

微波辐射促进杯芳烃酯类衍生物的快速合成

微波辐射条件下,以对叔丁基杯[6]、杯[8]芳烃为原料,采用氯乙酸乙酯为烃基化试剂,PEG-400为催化剂,可高效地制得下缘被酯基取代的产物.该方法较之传统方法,操作简单、反应时间大大缩短、污染减少.     

一种杯芳烃酯类衍生物的简洁合成方法

采用氯乙酸乙酯作烃基化试剂,杯芳烃在K2CO3／KI存在下于丙酮中回流4d,合成了4种杯芳烃酯类衍生物2a～2d,与文献法比较,方法不仅降低成本,减小毒性,还获得了与文献相近的反应收率。     

Synthesis and heavy metal ion adsorptivity of macroreticular chelating resins containing phosphono and carboxylic acid groups

Macroreticular copolymer beads were prepared by suspension polymerization of 4-vinylbenzyl chloride (VBC), divinylbenzene (DVB) and monomers with carboxylic ester groups like dibutyl maleate (DBM), dibutyl fumarate (DBF) and dibutyl itaconate (DBI) in the presence of toluene as diluent. The copolymer beads were phosphorylated at the chloromethylated phenyl rings with triethyl phosphite and hydrolyzed by an aqueous sodium hydroxide solution; the hydrolysis on the bead surface converted carboxylic ester/phosphonate groups into carboxylic acid/phosphono groups, respectively. The investigations on the metal ion chelation characteristics of the H-form copolymer beads revealed that they have good adsorptivity toward heavy metal ions like Pb²⁺, Cd²⁺ and Cu²⁺, and poor adsorptivity toward ions like Hg²⁺ and UO₂²⁺. The adsorptivity caused by the three carboxylic ester monomer derivatives was in the order DBM > DBI > DBF. Especially, the Na-form copolymer beads neutralized by alkali treatment were very available for the adsorption of all the metal ions under investigation.     

咪唑并[1, 2-a]吡啶甲酸衍生物的合成与表征

以3-三氟甲基-2-氨基吡啶为原料,通过NBS选择性溴化,再与溴代丙酮酸甲酯通过“一锅法”进行烷基化-环化反应,之后经选择性氯化、Suzuki偶联反应和水解,合成了咪唑并[1,2-a]吡啶甲酸衍生物。反应总收率达到36.5%。并对Suzuki偶联反应的催化剂和反应条件进行了探讨。     

Sorption of palladium(II) using organophosphorus derivatives based onthiacalix[4]arene impregnated resins from hydrochloric media

The sorption kinetics of Pd(II) from hydrochloric acid solutions by 1 and 2 impregnated Amberlite XAD-7 resins (3 and 4) have been systematically studied. Both impregnated resins selectively and efficiently adsorb Pd(II) from single metal solution and automotive catalyst residue solution. In comparison between 3 and 4, 4 showed more efficiency toward Pd(II) with respect to contact time, loading, and stripping capacities. 3 and 4 were characterized by XRD and SEM analyses before and after Pd(II) sorption. We also studied the reusability of 3 and 4 and both the resins offer excellent performance for three times.     

Adsorption of N-phenylmaleimide and its derivatives on iron electrodes in sulfuric acid solutions

The adsorption of N-(phenyl)maleimide and its derivatives on iron electrodes in sulfuric acid medium has been studied by the capacitance method. The process investigated is well described by Frumkin's isotherm. The adsorption parameters characterizing the interaction forces between the species in the adsorbed layer, the area occupied by each species and the maximum surface excess have been calculated on the basis of this isotherm. Combining data from the electrochemical method with quantum-chemical calculations of the chemical structure and the partial electronic charges of the compounds studied a mechanism of adsorption on the iron surface is proposed. The inhibiting effect observed is explained in relation to the adsorption behaviour.     

NMR structural elucidation of amino resins

Urea formaldehyde, melamine formaldehyde, and melamine urea formaldehyde (MUF) are important industrial amino resins that find application in numerous diverse areas, most notably in the bonding of wood products. To understand the physical properties of these amino resins and, hence, optimize their performance, a knowledge of their chemical structure is necessary. This article reports the use of NMR spectroscopy to acquire this information in the solid and liquid states. ¹³C‐NMR experiments, supported and augmented by ¹H‐NMR and ¹⁵N‐NMR results, showed that the two stages of resin synthesis, methylolation followed by condensation, occurred in each type of resin. However, in the various MUF samples analyzed, the second step appeared to be predominantly the self‐condensation of melamine and urea rather than the cocondensation of melamine and urea. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3504–3512, 2004     

大孔吸附树脂对红霉素的平衡吸附行为及其热力学性质

引言 红霉素(EM)是临床应用较多的一种大环内酯类抗生素,随着一些疗效更好的半合成衍生物的开发,红霉素原料需求呈现增长趋势.     

Efficiently removing phenols from aqueous solution using amino acid functionalized D301 resins

ABSTRACT

Amino acid functionalized D301 resins (Tyr-D301, Phe-D301, and Ala-D301) are successfully prepared to remove phenols. The influences of adsorption condition on adsorption ability and the practical application value are investigated. The functionalized D301 resins possess strong adsorption ability toward phenol by ways of hydrogen bond interaction. The adsorption capacity of Tyr-D301, Phe-D301, and Ala-D301 is 388.2, 368.4, and 321.5 mg· g^?1 at 293 K and pH of 2, respectively. The adsorption process could be described satisfactorily by Lagergren-first-order model and Langmuir model. The rate constant is 0.057, 0.042, and 0.035 min^?1, respectively. The functionalized D301 can be used to dispose wastewater containing phenols.     

氨基丙二醇功能化硼螯合树脂的制备及其硼酸吸附性能

分别用3-氨基-1,2-丙二醇（3-APD）和2-氨基-1,3-丙二醇（2-APD）对多孔氯甲基聚苯乙烯树脂（CMPS）进行修饰,制备得到含邻、间位二羟基官能团的硼螯合树脂：PS-3-APD和PS-2-APD。用傅里叶红外光谱仪（FTIR）、元素分析仪（EA）、压汞仪（MIP）和激光粒度仪（LPS）对材料进行表征,确认功能单体成功接枝于氯球上。对两种树脂进行了静态提硼性能研究,分别考察了原料液pH、初始硼酸浓度、外来金属离子对硼酸吸附量的影响,当溶液pH为9.15～9.20时,两种树脂对硼酸吸附量最大;溶液中Na⁺、Mg²⁺、Ca²⁺的存在会一定程度削弱树脂对硼酸吸附性能。吸附动力学表明其吸附速率较快,且均满足准二级动力学模型。与Freundlich相比,吸附等温线更符合Langmuir模型,拟合得到的理论最大吸附量分别为0.730mmol/g和0.868mmol/g。本文对未来新型硼螯合树脂的开发及工业化应用提供参考和指导。