Enzymatic Ring‐Opening Polymerization of Oxiranes and Dicarboxylic Anhydrides

Oxiranes, such as glycidyl phenyl ether, benzyl glycidate, glycidyl methyl ether, and styrene oxide, were copolymerized with dicarboxylic anhydrides, such as succinic anhydride, phthalic anhydride, and maleic anhydride, by the action of an enzyme in a stepwise reaction to produce the corresponding polyesters containing some ether linkages having a maximum M _w of 13 500. Oxiranes, such as glycidol and glycidyl phenyl ether, were also homopolymerized and copolymerized with other oxiranes by the enzyme to produce the corresponding polyethers.

Enzymatic polymerization of oxiranes and dicarboxylic anhydrides.     

Selective cleavage of the linear ether bond in benzyl glycidyl ether and triphenylmethyl glycidyl ether by potassium alkalide as two-electron-transfer reagent

The linear ether bond was exclusively cleaved in benzyl glycidyl ether and triphenylmethyl glycidyl ether under the influence of K⁻, K⁺(15-crown-5)₂ (1), whereas the strongly strained three-membered oxacyclic ring remained undisturbed. Potassium glycidoxide and benzylpotassium were found as the primary reaction products of benzyl glycidyl ether with 1. Subsequently, benzylpotassium reacted with benzyl glycidyl ether giving the next potassium glycidoxide molecule and bibenzyl. Benzyl phenyl ether was used as a model compound to explain the mechanism of bibenzyl formation. The reaction of triphenylmethyl glycidyl ether with 1 resulted in potassium glycidoxide and stable triphenylmethylpotassium. After treating with a quenching agent a new glycidyl ether or glycidyl ester was obtained from potassium glycidoxide. These results were found when the reaction occurred at the excess of glycidyl ether. In another case, i.e. at the excess of 1 further reactions took place with the participation of potassium anions and various new compounds were observed in the reaction mixture after benzylation or methylation. Thus, the method of substrates delivery influences the course of studied processes in a decisive way.     

Kinetics of Photocationically Curable Formulations Involving Glycerol Diglycidyl Ether and Phenyl Glycidyl Ether

Kinetic analysis of formulations based on glycerol diglycidyl ether and phenyl glycidyl ether were carried out in the presence of sulfonium salt as initiator at 35 mW cm^?2using photo differential scanning calorimeter and the final conversion was found to increase with an increase in phenyl glycidyl ether content. The effects of formulation monomer ratios at three different temperatures were studied. The variations in the observed kinetic parameters can be related to increase in mobility of reactive species with temperature, distance of counter ion from the propagating cationic center, as well as extent of crosslinking reaction which controlled the course and duration of the reaction. The applicability of autocatalytic kinetic model was also evaluated and the system underwent early gelation and the activation energy decreased with an increase in phenyl glycidyl ether content. Analysis of stable photocured films containing glycerol diglycidyl ether and phenyl glycidyl ether showed better thermal stability than rigid films obtained with glycerol diglycidyl ether.     

Propargyl‐Functional Aliphatic Polycarbonate Obtained from Carbon Dioxide and Glycidyl Propargyl Ether

The synthesis of propargyl‐functional poly(carbonate)s with different content of glycidyl propargyl ether (GPE) units is achieved via the copolymerization of propargyl glycidyl ether and carbon dioxide. A new type of functional poly(carbonate) synthesized directly from CO₂ and the glycidyl ether is obtained. The resulting polymers show moderate polydispersities in the range of 1.6–2.5 and molecular weights in the range of 7000–10 500 g mol⁻¹. The synthesized copolymers with varying number of alkyne functionalities and benzyl azide are used for the copper‐catalyzed Huisgen‐1,3‐dipolar addition. Moreover, the presence of vicinal alkyne groups opens a general pathway to produce functional aliphatic poly(carbonate)s from a single polymer scaffold.

     

Synthesis and oxoanions (dichromate/arsenate) sorption study of N-methylglucamine derivative of calix[4]arene immobilized onto poly[(phenyl glycidyl ether)-co-formaldehyde]

The article describes synthesis as well as the evaluation of sorption properties of new N-methylglucamine substituted calix[4]arene and its poly[(phenyl glycidyl ether)-co-formaldehyde] immobilized product. Firstly, 5,17-bis-[(N-methylglucamine)methyl]-25,26,27,28-tetrahydroxy-calix[4]arene (3) was synthesized by the treatment of calix[4]arene with a secondary amine N-methylglucamine and formaldehyde via Mannich reaction. The immobilization of 3 onto poly[(phenyl glycidyl ether)-co-formaldehyde] to form calixarene based polymer (4) was carried out under suitable reaction conditions via nucleophilic substitution reaction. All the new compounds were characterized by a combination of FT-IR, ¹H-NMR spectroscopic and elemental analysis techniques. The sorption studies of 4 reveal that it is an excellent material for the removal of toxic oxoanions especially arsenate from aqueous environment. To understand the selectivity of 4, we also examined the retention of dichromate anions in the presence of Cl^?, NO₃ ^? and SO₄ ^2? anions at pH 1.5.     

Study of chemical processes in the modification of epoxide polymers by aluminum oxide

The processes occurring during the modification of epoxy polymers by various polymorphic aluminum oxide modifications (γ-AlO(OH), γ-Al₂O₃, α-Al₂O₃) with epoxy groups were studied by the methods of IR Fourier spectroscopy, chemical analysis, and differential scanning calorimetry (DSC) by an example of a model compound (phenyl glycidyl ether). Two types of interactions were revealed: a direct chemical reaction of phenyl glycidyl ether with the surface hydroxy groups of alyminum oxide, and phenyl glycidyl ether homopolymerization. By processing by graphical method the data of chemical analysis on the diminishing in amount of epoxy groups in the course of the polycondensation reaction the value of activation energy 106–110 kJ mol⁻¹ of the process of phenyl glycidyl ether interaction with aluminum γ-oxide was determined.     

缩水甘油苯基醚-缩水甘油正丁基醚共聚物磺酸钠的合成及表面活性

缩水甘油苯基醚-缩水甘油正丁基醚共聚物磺酸钠的合成及表面活性;缩水甘油苯基醚-缩水甘油正丁基醚共聚物磺酸钠; 合成; 表面性质; 胶束     

Dichlorocyclopropanation of chloro-substituted vinyl phenyl ethers

Conclusions The reaction of chloro-substituted vinyl phenyl ethers with dichlorocarbene generated by the thermolysis of phenyl(trichloromethyl)mercury leads to the corresponding gem-dichlorocyclopropyl derivatives while the reaction of cis--chlorovinyl phenyl ether with chloroform and alkali under phase transfer catalysis conditions gives -trichloromethyl--chloroethyl phenyl ether.Deceased.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 222–224, January, 1985.     

Capacites calorifiques de durcisseurs amines et resines epoxydes

Heat capacities of some amines (aniline, N-methyl aniline, meta-phenylene diamine, diamino diphenyl methane, diamino diphenyl sulfone and diamino diphenyl oxide) and two epoxy resins (phenyl glycidyl ether and diglycidyl ether of bisphenol A) have been determined in the solid and liquid states versus temperature. The heat capacity increments related to the functional groups have been evaluated compared to references like benzene, aniline and phenyl glycidyl ether.     

Kinetic and Quantum-Chemical Study of Oxirane Ring Cleavage with Acids

Kinetic and thermodynamic parameters of the reactions of phenyl glycidyl ether and epichlorohydrin with bis(alkylpolyethylene glycol) ether of orthophosphorus acid (oxyphos KD-6) are established. It is shown that the difference in the reactivity of the oxiranes is caused by the electronic effects of substituents and the protonation by the phenolic oxygen atom of phenyl glycidyl ether. Basic solvents decrease the reactivity of the systems. Based on AM1 semiempirical quantum-chemical calculations, a hydroxycarbocation mechanism of the oxirane ring opening was proposed, involving initial formation of unstable cis- and trans-oxonium structures.     

Influence of solvent on conformational equilibrium in phenyl glycidyl ether

The conformational equilibrium in phenyl glycidyl ether in aprotic solvents was studied by the PMR method over a broad range of changes in the values of the dielectric constant. It was shown that the parameters of the multiplet of noncyclic methylene protons in the PMR spectrum of phenyl glycidyl ether are a sensitive indicator of the position of the conformational equilibrium in the glycidyl fragment. The specific interaction of the molecules of aromatic solvents with the epoxide ring has been discovered.Translated from Teoreticheskaya i Eksperimental'naya Khimiya, Vol. 21, No. 2, pp. 245–247, March–April, 1985.     

N-p-toluenesulfonyl-2-oxazolidones Via the cycloaddition reaction of p-tolucnesulfonyl isocyanate and epoxides

The reaction of styrene oxide and phenyl glycidyl ether with p-toluenesulfonyl isocyanate, employing a hydrocarbon-soluble adduct of tributylphosphine oxide and lithium bromide as catalyst, results in excellent yields of the N-p-toluenesulfonyl-2-oxazoIidones. The 5-isomeric-2-oxazolidone is obtained from phenyl glycidyl ether, but in contrast to conventional isocyanates, the p-toluenesulfonyl isocyanate, upon reaction with styrene oxide, produces the 4-isomeric 2-oxazolidone as the major product. The effect of the N-sulfonyl group on the nmr spectra of 2-oxazolidones is discussed.     

Thioether‐Bearing Hyperbranched Polyether Polyols with Methionine‐Like Side‐Chains: A Versatile Platform for Orthogonal Functionalization

The synthesis of thioether‐bearing hyperbranched polyether polyols based on an AB/AB₂ type copolymerization (cyclic latent monomers) is introduced. The polymers are prepared by anionic ring‐opening multibranching copolymerization of glycidol and 2‐(methylthio)ethyl glycidyl ether (MTEGE), which is conveniently accessible in a single etherification step. Slow monomer addition provides control over molecular weights. Moderate dispersities (Đ = 1.48–1.85) are obtained, given the hyperbranched structure. In situ ¹H NMR copolymerization kinetics reveal reactivity ratios of r _G = 3.7 and r _MTEGE = 0.27. Using slow monomer addition, copolymer composition can be systematically varied, allowing for the adjustment of the hydroxyl/thioether ratio, the degree of branching (DB = 0.36–0.48), thermal properties, and cloud point temperatures in aqueous solution in the range of 29–75 °C. Thioether oxidation to sulfoxides enables to tailor the copolymers' solubility profile. Use of these copolymers as a versatile, multifunctional platform for orthogonal modification is highlighted. The methyl sulfide groups can be selectively alkoxylated, using propylene oxide, allyl glycidyl ether, or furfuryl glycidyl ether, resulting in functional hyperbranched polyelectrolytes. Reaction of the alcohol groups with benzyl isocyanate demonstrates successful orthogonal functionalization.

     

New facts concerning the reaction of K, K(15-crown-5)2 with phenyl glycidyl ether: unexpected formation of potassium cyclopropoxide

A new mechanism of the reaction of K⁻, K⁺(15-crown-5)₂ with phenyl glycidyl ether is presented. The linear ether bond is attacked only to a small extent, if at all. As the main reaction path the oxirane bond in the β-position is cleaved, followed by the γ-elimination of potassium phenoxide and the formation of potassium cyclopropoxide. Crown ether ring opening also occurs in reactions with organometallic intermediates.     

Reaction of glycidyl phenyl ether with imines: A model study of latent hardeners of epoxy resins in the presence of water

The hydrolyses of several imines and their reactions with glycidyl phenyl ether were examined under highly humid conditions as a model study for the development of water‐initiated hardeners for epoxy resins. Diethyl ketone‐based imines were hydrolyzed more efficiently than methyl isobutyl ketone‐based imines. The reactions of glycidyl phenyl ether with the imines depended on their hydrolysis rates and the basicity of the amines generated from them. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 971–975, 2002     

Anhydride curing of epoxy resins via chain reaction

In contrast to common curing reactions, the anhydride curing of epoxies follows a living anionic chain growth. The resulting consequences of this mechanism, i.e. (1) DP_n = a[M_o]/[I_o], (2) first-order kinetics and (3) Poisson chain-length distribution were tested with the phenyl glycidyl ether/phthalic acid anhydride system, using l-methyl imidazole. Overall agreement was found and the observed deviations could be explained with a modified Poisson process. Conformational properties of the resins were measured by static and dynamic light scattering and by viscometry. These were compared with the quantities of a corresponding branched system prepared with a mixture of phenyl glycidyl ether and bisphenol-A diglycidyl ether. Typical deviations to smaller dimensions were observed at high molar masses as a result of increasing branching.     

纳米SiO2改性苯基缩水甘油醚丙烯酸酯的紫外光固化性能研究

以苯基缩水甘油醚（PGE）和丙烯酸（AA）为原料,三苯基膦为催化剂,4-甲氧基苯酚为抑制剂,合成了一种新型光敏预聚物苯基缩水甘油醚丙烯酸酯（PGEA）。然后用十六烷基三甲基溴化铵处理纳米SiO₂,并用硅烷偶联剂γ-甲基丙烯酰氧基丙基三甲氧基硅烷（KH-570）进行表面改性,并加入到预聚物PGEA中,制成紫外纳米复合涂层。用扫描电子显微镜（SEM）发现涂层含量小于5%时,改性纳米SiO₂的分散效果较好。用扫描原子力显微镜（AFM）观察到固化膜表面光滑。而适量的改性纳米SiO₂可以提高紫外光固化材料的拉伸强度、伸长率和冲击强度。     

Catalytic degradation of polystyrene using HUSY catalysts

Summary The addition of carbon dioxide to phenyl glycidyl ether (PGE) was investigated in a semi-batch reactor using immobilized quaternary ammonium chloride catalysts. Five different catalysts were prepared with the following supports : (1) soluble poly(ST-<Emphasis Type=Italic>co</Emphasis>-VBC) [C1], (2) insoluble poly(ST-DVB-VBC) [C2], (3) macroporous poly(ST-DVB-VBC) [C3], (4) poly(ST-<Emphasis Type=Italic>co</Emphasis>-VBC)-MMT [C4] (5) modified MCM-41 [C5]. The addition of carbon dioxide to PGE can be considered as a pseudo-first order process with respect to the concentration of PGE. The pseudo-first order rate constant for the catalysts decreased in the series C1&gt;C3&gt;C2&gt;C4&gt;C5. The activation energy for C1 to C5 catalysts was 8.6, 20.9, 19.9, 23.9, and 26.8 kJ/mol, respectively. The immobilized catalysts can be reused in least 4 successive runs without any considerable loss of their initial reactivities.     

Novel photocurable monomers: The synthesis of difunctional vinyl ethers with a phosphonate group and difunctional 1‐propenyl ethers with a phosphonate group and their photoinitiated cationic polymerization

Phosphorus‐containing vinyl ether monomers and 1‐propenyl ether monomers were prepared by the regioselective addition reaction of glycidyl vinyl ether (GVE) or 1‐propenyl glycidyl ether with diaryl phosphonates with quaternary onium salts as catalysts. The reaction of GVE with bis(4‐chlorophenyl) phenylphosphonate gave bis[1‐(4‐chlorophenoxy methyl)‐2‐(vinyloxy)ethyl]phenylphosphonate in a 68% yield. The structures of the resulting phosphorus‐containing vinyl ether monomers and 1‐propenyl ether monomers were confirmed by IR and ¹H NMR spectra and elemental analysis. Photoinitiated cationic polymerizations of the resulting phosphorus‐containing vinyl ether monomers and 1‐propenyl ether monomers were investigated with photoacid generators. The polymerization of vinyl ether groups and 1‐propenyl ether groups of the obtained monomers proceeded very smoothly with a sulfonium‐type cationic photoinitiator, bis[4‐(diphenylsulfonio)phenyl]sulfide‐bis(hexafluorophosphate), upon UV irradiation. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3105–3115, 2005