Preparation of ion-exchange celluloses. I. Anion exchange celluloses

Cellulose–poly(glycidyl methacrylate) graft copolymer (CPGMA) was treated with ammonia (AH), ethylamine (EA), diethylamine (DEA), and triethylamine (TEA). Factors affecting the reaction, such as reaction duration, temperature, liquor ratio, pH, and aminating agent/epoxide molar ratio were studied. A mechanism of the reaction was suggested. The anion exchange celluloses were characterized by studying its capacity, potentiometric titration, and durability to use. Potentiometric titration of the produced anion exchangers has been studied and pK_b values were found to be 6.1, 7.6, and 8.9 for DEA–CPGMA, EA–CPGMA, and AH–CPGMA, respectively.     

Glycidyl esters. IV. Hydration of glycidyl stearate

The acid-catalyzed conversion of glycidyl stearate to monostearin has been investigated. By use of au essentially nonaqueous reaction medium and a two-step procedure, high yields of monostearin were obtained at 15–20C in brief reaction periods, while avoiding ester hydrolysis. Distearin was found to be a by-product. The influence of solvent, reaction temperature, and type of acid catalyst upon the relative amounts of monostearin and distearin produced were studied. A possible reaction path leading to the formation of distearin is proposed. Part III in press. Part II, JAOCS,38, 194 (1961). A laboratory of the E. Utiliz. Res. & Dev. Div., ARS, U.S.D.A.     

Glycidyl esters. II. Synthesis of esters of commercial and pure fatty acids

The reaction of salts of earboxylic acids with epichlorohydrin in the presence of quaternary ammonium halides to form glycidyl esters has been demonstrated to be applieable to a variety of acids derived from fats, including commercial mixtures. The glycidyl esters of pelargonic, lauric, oleic, dimerized linoleic, ricinoleic, behenic, and sebacic acids as well as those of the fatty acids derived from tallow, wool wax, and soya oil have been prepared in 80–95% yields and purities. Eastern Utilization Research and Development Division, Agricultural Research Service, U.S. Department of Agriculture.     

Reaktive polymere. V. Metallkomplexe polymergebundener schiffscher basen

The complexes of bivalent copper and cobalt with salicylidene ethylene diamine ligands bounded to macroporous glycidyl methacrylate-ethylene dimethacrylate copolymers have been studied, and characterised by I.R. spectra. The transfer of oxygen by cobalt complex has been followed.     

Kinetics of addition of acetic acid to epichlorohydrin in the presence of alkali metal acetates

The kinetics of the reaction between acetic acid and epichlorohydrin in the presence of lithium, sodium and potassium acetates have been studied. The composition of the reaction mixture was followed chromatographically. Beside the two isomeric products of addition of epichlorohydrin to acetic acid, the presence was found of glycidyl acetate, glycerine dichlorohydrin and other products of parallel and subsequent reactions between the substrates and chlorohydroxyesters. A mechanism of the reaction, which takes into account the formation of the identified compounds has been proposed and a set of appropriate differential and balance equations developed. The rate constants for individual reactions as well as the catalysts used have been determined.     

Photo-crosslinkable polymers with benzylideneacetophenone (chalkone) structure in the side chains

Four soluble types of polymers have been synthesized by grafting 4- and 4′-chalkonyl glycidyl ethers onto an aromatic polyamine (aniline–formaldehyde linear resin) and a polyamide (condensation product of dimerized linseed oil and an aliphatic polyamine) to obtain photo-crosslinkable chalkone structure in the side chains which are also expected to contain one ? OH group each. The completion of grafting reactions has been followed by the disappearance of the epoxide absorption around 918 cm^?1. The characterization of the resins was done by melting point, solubility, and IR measurements. Irradiation was carried out with a 100-watt Hanovia high-pressure mercury are lamp. Irradiated samples were studied by UV spectral measurements and their insolubility in CHCl₃. It was observed that polymers grafted with 4′-chalkonyl glycidyl ether possibly undergo both isomerization and crosslinking reactions under UV irradiation while those grafted with 4-chalkonyl glycidyl ether undergo crosslinking reaction predominantly.     

Investigation of the elementary reactions in the synthesis of poly(hydroxethers) in dipolar,aprotic solvents

The effect of the hydroxyl groups of various phenols on the course of the reaction of their alkali metal salts with epichlorohydrin in dipolar, aprotic solvents has been studied. It was found that the presence of phenols in the system leads to the formation of a complex salt of the type (ArO … H … OAr)^?Mt⁺, and to a considerable decrease in the reaction rate. The mechanism of the reaction of chlorohydrin ethers of phenols with alkali metal phenolates was also studied. The effect of various factors on the course of the reaction of glycidyl ethers with phenols was determined by kinetic measurements.     

An Investigation of the Reaction of Epoxides with Wood

Abstract

The reaction of wood with two functionalised epoxides, allyl glycidyl ether (AGE) and glycidyl methacrylate (GMA), has been studied. For the reaction with whole wood samples of Scots Pine (Pinus sylvestris), maximum weight percent gains (WPG's) of 20% (GMA) and 7% (AGE) were obtained using pyridine as a solvent/catalyst. However, reaction of the epoxides with thermomechanically pulped Spruce fibre yielded WPG's of 15% (GMA) and 0% (AGE) under the same reaction conditions. In addition, the use of hydroquinone as an inhibitor of polymerisation yielded variable results. The observed WPG's obtained were found to be strongly influenced by the clean-up procedure used at the end of the reaction. The results suggest that, under the conditions used in this study, no reaction with the wood hydroxyl groups is occurring but that homopolymerisation of the epoxides is responsible for the observed data.     

甲基丙烯酸缩水甘油酯的合成研究

采用二步法合成了甲基丙烯酸缩水甘油酯,研究了第一步反应过程4种溶剂对甲基丙烯酸钠盐形成的影响,探讨了第二步反应过程不同相转移催化剂、反应温度及所合成钠盐中碱过量比率与产物收率的关系,对最后产物进行了分析和表征。结果表明,合成反应第一步可使用水为溶剂,碱过量10%,第二步反应中,使用三乙基苄基氯化铵为催化剂,控制反应温度105℃～110℃,反应3.0h,可使GMA收率达到80.5%。     

Photopolymerization of carbazolyloxiranes

Photopolymerizations of 1-allyloxy-3-(carbazol-9-yl)-2-propanol glycidyl ether and 1-(carbazol-9-yl)-4-oxa-2-pentanol glycidyl ether with diaryliodonium salts in solution and in bulk are reported. These reactions give oligomers of degree of polymerization 4–6. The influence of the functional groups of the monomers on the rate of polymerization, conversion limit and molecular weight is discussed. The effects of photoinitiator and reaction media on these factors have also been studied.     

Curing of epoxy resins with dicyandiamide

Summary The mechanism of the epoxy resin curing with dicyandiamide was studied using the model phenyl glycidyl ether and different substituted dicyandiamides. Some reaction products were isolated by HPLC and characterized by FTIR and Carbon-13 NMR spectroscopy. A reaction pathway is proposed discussing the formation of cyclic structures, carbonyl groups and oligomerization products of the glycidyl ether.     

微波辐射相转移催化合成十二烷基缩水甘油醚

采用微波辐射技术,以四丁基溴化铵为相转移催化剂催化合成了十二烷基缩水甘油醚,研究了微波功率、辐射时间、反应物配比对反应产物收率的影响。实验结果表明,适当的微波辐射可以加速十二烷基缩水甘油醚的合成反应,而且产率高,操作简便。     

Catalytic performance of pyridinium salt ionic liquid in the synthesis of cyclic carbonate from carbon dioxide and butyl glycidyl ether

The catalytic performance of pyridinium salt ionic liquids in the reaction of butyl glycidyl ether and carbon dioxide was investigated in this study. The catalytic activity was studied in a batch reactor with different 1-alkylpyridinium salt ionic liquids at 60–140°C. The conversion of butyl glycidyl ether was affected by the structure of the ionic liquid; the one with the cation of bulkier alkyl chain length showed better reactivity. The effect of carbon dioxide pressure, reaction temperature and zinc bromide co-catalyst on this reaction was also discussed.     

Reaction of glycidyl benzoate with acid in the presence of tertiary amines as the catalyst

The reaction of epoxides with carboxylic acids catalysed by tertiary amines has been discussed. The mechanism of the reaction has been deduced and confirmed, using experimental results, on the example of the reaction of glycidyl benzoate with benzoic acid in xylene, catalysed by benzyldimethylamine. The reaction occurs via a combined ionic mechanism as well as via a complex formation, thus explaining the abnormal dependence of the reaction constant on the dielectric constant of the milieu and the found non-integer orders of reaction with respect to the amine and to the acid.     

缩水甘油月桂酸酯的制备

论述了由环氧氯丙烷与月桂酸钠在相转移催化条件下反应制取缩水甘油月桂酸酯的方法。产率在９０％以上。     

Microwave assisted preparation of quaternized chitosan catalyst for the cycloaddition of CO2 and epoxides

An efficient method of utilizing microwave irradiation for the quaternization of chitosan (QCHT) has been investigated. QCHT catalysts have been characterized by various physicochemical methods such as FT-IR, XRD, XPS, TGA, EDS, SEM, EA, and BET. They exhibited excellent activity for the solvent-free cycloaddition of CO₂ and allyl glycidyl ether (AGE). The influences of alkyl chain length and anion of the QCHT catalyst on the cycloaddition reactivity were studied. The effects of reaction parameters such as catalyst amount, reaction time, temperature, and CO₂ pressure were also investigated. QCHT prepared by microwave irradiation exhibited higher catalytic activity than the conventional QCHT.     

Polymerization of p-cresyl glycidyl ether catalyzed by imidazoles I. The influence of the imidazole concentration,the reaction temperature,and the presence of isopropanol on the polymerization

The polymerization of p-cresyl glycidyl ether catalyzed by imidazoles has been investigated as a model reaction for the polymerization of technical epoxy resins. The dependence of oligomer yield on time, temperature, and imidazole concentration, the distribution of the polymerization degrees, and the influence of isopropanol have been studied. The reaction rate and the average degree of polymerization are affected by the presence or absence of a secondary nitrogen on the imidazole, i.e., different results are obtained when 2-ethyl, 4-methyl imidazole (EMI) or 1-methyl imidazole (1-MIA) are used. 1-MIA seems to be “precursor” of the catalyst rather than a catalyst by itself. The comparisons of CGE polymerizations catalyzed by 1-MIA in the absence and presence of isopropanol show only quantitative differences: The polymerization in the presence of isopropanol is faster, and the average degree of polymerization is shifted to higher values. The activation energies of CGE polymerizations catalyzed by different imidazoles have been determined.     

Thioether glycidyl resins. II. Products of condensation of bis(4-mercaptomethylphenyl) ether and bis(4-mercaptomethylphenyl)methane with epichlorohydrin

New thioether glycidyl resins produced by condensation of bis(4-mercaptomethylphenyl) ether and bis(4-mercaptomethylphenyl)methane with epichlorohydrin were obtained by heterophase alkaline condensation in water and isopropyl alcohol solution. To define the optimal conditions of condensation, the following factors that influence the process were studied: the mole ratios of epichlorohydrin–mercaptan, alcohol–mercaptan, alkaline hydroxide–mercaptan. For all reaction products, yield, epoxide content, and chlorine content were determined. The structure of thioether glycidyl resins with the highest epoxide content was determined by elemental analysis and infrared and NMR spectra. The physical and chemical properties were defined. Some properties of the resins, cured chemically or thermally with different curatives, and thermal and mechanical properties of the cured compounds were determined.     

The alkyl glycidyl ether as synthetic building blocks

Alkyl glycidyl ether is one of the most useful key materials for industrial applications because the addition reaction of various kinds of nucleophilic reagents to the reactive epoxy bond of the glycidyl ethers has led to glyceryl ether derivatives. Glyceryl ether exhibits many interesting physical and pharmacological properties. The alkyl glycidyl ether can presently be produced at an industrial scale under the phase-transfer catalytic Williamson ether synthesis. We have reviwwed some addition reactions of the alkyl glycidyl ether and possibilities for use as the building blocks for the syntheses of surfactants, pharmaceuticals, etc. that contain glyceryl ether skeletons. Typical examples of alkyl glyceryl ether derivatives include: amino ether as cosmetic material, and isodiglycerin mono- and dialkyl ethers and triglycerin monoalkyl ether as a cosmetic or a pharmacologically useful material, respectively. Another interesting reaction is the rearrangement of the epoxy bond of the alkyl glycidyl ether, which gives alkoxy ketone in a one-pot synthesis.     

Preparation of poly(glycidyl methacrylate) grafted sulfonamide based polystyrene resin with tertiary amine for the removal of dye from water

Poly(glycidyl methacrylate) was grafted onto crosslinked poly(styrene) beads through the 2-chloroethyl sulphonamide (CSA) groups present in the resin using ATRP polymerization method. A beaded polymer with a poly(glycidyl methacrylate) surface shell was prepared in three steps, starting from poly(styrene-DVB) (10% crosslinking) based beads with a particle size of 420–590 μm, according to the synthetic protocol; chlorosulfonation, sulfamidation with 2-chloroethylamine hydrochloride and grafting reaction of poly(glycidyl methacrylate).The polymeric resin was prepared with 147.8% of grafted glycidyl methacrylate and subsequent modified with diethyl amine to introduce tertiary amine groups. This resin has also been demonstrated to be an efficient dye sorbent, able to remove dye from water even at ppm levels. The dye sorption capacity under non-buffered conditions is around 0.90 g dye/g resin.