Polyaddition Of Bisphenol Research Articles

Zywice epoksydowe o zwiekszonym ciezarze czasteczkowym - synteza i charakterystyka termiczna

Increased molecular weight epoxy resins (EPzcc) were synthesized by polyaddition of bisphenol A and low molecular weight epoxy resin, in the presence of 2-methylimidazole (2-MI) as a catalyst. Reaction mixture was heated either conventionally or by microwave radiation. EPzcc preparation carried out using three various amounts of a catalyst (Table 1). The products obtained differed in epoxide equivalent value (LE) and secondary OH groups' (LOH) contents. The resins were cured with dicyandiamide (DCDA). The course of the process was monitored using DSC method (Table 2, Fig. 1 and 2). Investigations of EPzcc by thermogravimetry (Table 4 and 5, Fig. 3) showed that even though the initial temperature of resin decomposition slightly increased after curing, the thermal stability at elevated temperature was significantly worse than that characterizing the initial uncured resin.

Synthesis of photocrosslinkable hyperbranched polyesters and their film properties

AbstractHyperbranched polyesters with terminal methacryloyl groups (HBPEAc) were synthesized by the one‐pot polyaddition of bisphenol A diglycidyl ether and trimesic acid in the presence of methacrylic acid with a number‐average molecular weights of 5100–7700 in 70–83% yields. The photoradical polymerization of HBPEAc was examined in the presence of 2‐methyl‐1‐[4‐(methylthio)phenyl]‐2‐morpholinopropan‐2‐one (Irgacure 907®) as a photoinitiator in the film state upon UV irradiation to afford the corresponding cured films quantitatively. The crosslinking densities of the cured films of HBPEAc were higher than those of the corresponding linear ones, and birefringence cannot be detected for the cured films of HBPEAc because of their random structures. Furthermore, an alkaline‐developable hyperbranched polyester containing pendant carboxyl groups (HBPEAc‐COOH) was prepared by the addition reaction of HBPEAc with cis‐1,2,3,6‐tetrahydrophthalic anhydride, and its patterning properties were examined to give the resolution of a 55‐μm‐line and 275‐μm‐space pattern by UV irradiation with 700 mJ/cm2. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4642–4653, 2005

Microwave assisted synthesis and determination of chain branching in solid epoxy resins using 1H NMR spectrometry

The degree of branching in solid epoxy resins (epoxy value EV=0.11 mol/100 g) prepared under microwave and conventional conditions has been investigated by 1H NMR spectrometry. The applied method involves rapid reaction between trichloroacetyl isocyanate and hydroxyl groups incorporated in the epoxy resin structure. Solid epoxy resins were prepared by polyaddition of Bisphenol A (BPA) to a lower-molecular-weight (L-M) epoxy resin (Rütapox 0162, EV=0.57) in the presence of 2-methylimidazole (2-MI) as a catalyst. All the microwave reactions were performed in the multimode microwave reactor Plazmatronika-Poland with microwave frequency of 2.45 GHz and maximum of microwave power of 600 W. The results show that the degree of branching in resins synthesized under microwave irradiation is comparable with those obtained under conventional heating (i.e. 6–12%) and is not influenced by the reduction of reaction time.

Synthesis of elevated-molecular-weight epoxy resins with aid of microwaves

Summary — A new method of synthesis of elevated-molecular-weight (E-M) epoxy resins with desired epoxy-groups content, based on polyaddition of bisphenol A to a lower-molecular-weight (L-M) epoxy resin (epoxy value EV = 0.57 mol/100 g) under microwave irradiation in the presence of 2-methylimidazole, as a catalyst, was described. Syntheses were carried out in a multi-mode microwave reactor “Plazmatronika” (Poland) of microwave frequency 2.45 GHz and maximal microwave power 300 W. Analogical syntheses have been done using conventional heating for the comparison of the methods. Values of EV, M , M and M /M of the products obtained have been determined. The main advantage of the process is twofold reduction of reaction time of the processes carried at microwave reactors in comparison to

A Novel Synthesis of Poly(carbonate)s by the Polyaddition of Bis(epoxide)s with Diphenyl Carbonate

The synthesis of poly(carbonate)s with phenoxymethyl groups in their side chains by a polyaddition of bisphenol A diglycidyl ether (4a) with diphenyl carbonate (2) using quaternary onium salts or c...

A Novel Synthesis of Reactive Polycarbonates with Pendant Chloromethyl Groups by the Polyaddition of Bis(epoxide)s with 2,2‘-Bis[(4-chloroformyl)oxyphenyl]propane

The polyaddition of bisphenol A diglycidyl ether (4a) with 2,2'-bis[(4-chloroformyl)oxyphenyl]-propane (5) was examined using quaternary onium salts as catalysts. When the polyaddition was performed using catalysts containing Br - as a counteranion such as tetraphenylphosphonium bromide in chlorobenzene at 100 °C for 48 h, the corresponding poly(alkyl aryl carbonate) with high molecular weight (M n = 59 000) was obtained. It was found from the 1 H NMR and 13 C NMR spectra of the obtained polymer that the reaction proceeded regioselectively at the epoxy group of 4a to provide the polycarbonate with pendant chloromethyl groups. The polyaddition of various bis(epoxide)s with 5 also proceeded smoothly to give the corresponding poly(carbonate)s with high molecular weight in good yields. The chemical modification of the obtained poly(carbonate)s with pendant chloromethyl groups by the phase-transfer method was also investigated using nucleophiles such as potassium thiocyanate and potassium 3-phenyl-2,5-norbornadienecarboxylate.

Application of Phosphonium Ylides to Latent Catalysts. 2. Kinetic Study on the Thermal Latency of the Phosphonium Ylides in the Polyaddition of Bisphenol A Diglycidyl Ether with Bisphenol A

Substituent effects of phosphonium ylides Ph3PC(H)COR (1R) were kinetically studied in the reaction of glycidyl phenyl ether (GPE) with 2,6-dimethylphenol in the presence of the phosphonium ylide catalysts, (formylmethylene)triphenylphosphorane (1H), (acetylmethylene)triphenylphosphorane (1Me), (benzoylmethylene)triphenylphosphorane (1Ph), and (pivaloylmethylene)triphenylphosphorane (1tBu) for molecular design of excellent latent catalysts. Both the activation energy (Ea) and frequency factor (A) of the reaction increased with the bulkiness of the acyl group of 1. Further, the catalytic activity was examined in the polyaddition of bisphenol A diglycidyl ether with bisphenol A in the presence of phosphonium ylide catalysts. The catalytic activity decreased with the bulkiness of the acyl group of 1, but the latency, i.e., the starting temperature, of the epoxide conversion was little affected. On the other hand, the introduction of acetyl and cyano groups into the catalysts as the electron-withdrawing moiet...

Novel synthesis of polyphosphonates by the polyaddition of bis(epoxide) with diaryl phosphonates

The polyaddition of bisphenol A diglycidyl ether (BPGE) with bis(4-chlorophenyl) phenylphosphonate was carried out using quaternary onium salts or crown ether complexes as catalysts. When the polyaddition was performed using tetrabutylammonium chloride, tetrabutylphosphonium chloride, or 18-crown-6/KCl in N- methyl-2-pyrrolidone at 110°C for 48 h, the corresponding polyphosphonate with moderated molecular weights was obtained in 88–96% yields. The structure of the resulting polyphosphonate was confirmed by IR and 1H-NMR spectra. The polyaddition of BPGE with various diaryl phosphonates also proceeded very smoothly to produce the corresponding polyphosphonates with moderate molecular weights. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 959–965, 1999

Novel synthesis of polyethers by the polyaddition of bis(epoxide)s with bis(phosphinate)s

The polyaddition of bisphenol A diglycidyl ether with bis[4-(P,P-diphenylphosphinyloxy)phenyl] sulfone catalyzed by quaternary onium salt, such as tetrabutylammonium chloride afforded a new phosphorus-containing polyether with good solubility in common organic solvents. Having studied various factors affecting the reaction, such as temperature, catalyst concentration, reaction time, etc., an appropriate polyaddition condition was suggested as using 5 mol % of suitable quaternary ammonium or phosphonium salt in polar solvent at 150°C within 25 h in an ampule for producing high molecular weight polymer. A number of polyethers bearing pendent phosphinate ester groups from the polyaddition of certain bis(epoxide)s and bis(phosphinate)s were synthesized under the above condition and characterized by GPC, IR, and NMR.

Synthesis of polysulfonates containing reactive pendant chloromethyl groups by the polyaddition of bisepoxides with disulfonyl chlorides

Polysulfonates with reactive pendant chloromethyl groups were synthesized by polyadditions of bisepoxides with disulfonyl chlorides. The polyaddition of bisphenol A diglycidyl ether (BPGE) with m-benzene disulfonyl chloride (m-BDSC) occurred in anisole without any catalyst at 130°C for 24 h. However, polymer with high molecular weight was not obtained. On the other hand, the polyadditions of BPGE with m-BDSC proceeded very smoothly with high yield (81–91%) to give polymers with relatively high molecular weights in anisole at 130°C for 24 h when quaternary phosphonium salts were used as catalysts. The polyaddition was also enhanced by the addition of certain crown ether complexes. However, the catalytic activity of these compounds was less than those of quaternary phosphonium salts. Furthermore, polyadditions of certain bisepoxides with disulfonyl chlorides were also carried out to produce the corresponding polymers under the same reaction conditions. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 249–256, 1998

New Synthesis of Poly(S-thioester)s by Regioselective Addition Reaction of Bis(thiirane)s with Diacyl Chlorides Using Quaternary Onium Salts

Poly(S-thioester)s were successfully synthesized by a new addition reaction of bis(thiirane)s with diacyl chlorides catalyzed by quaternary onium salts or crown ether complexes. The polyaddition of Bisphenol A bis(2,3-epithiopropyl) ether (BPTE) or butanediol bis(2,3-epithiopropyl) ether with certain diacyl chlorides proceeded smoothly using quaternary onium chlorides to give the corresponding poly(S-thioester)s with relatively high molecular weights. When the reaction of BPTE with terephthaloyl chloride or isophthaloyl chloride was carried out using 5 mol % of tetrabutylammonium chloride (TBAC) or tetrabutylphosphonium chloride (TBPC) in anisole at 90 °C for 24 h, the poly(S-thioester) with a number-average molecular weight of 40 000 was obtained. The reaction was enhanced more efficiently in aromatic solvents such as toluene or anisole than in aprotic polar solvents. It was proven that the reaction proceeded regioselectively to give the poly(S-thioester)s with the pendant chloromethyl group, which was introduced simultaneously with the formation of a S-thioester linkage in the polymer backbone during the reaction.

New Synthesis of Poly(silyl ether) and Poly(germyl ether) by Addition Reactions of Bisepoxides with Dimethyldiphenoxysilane and Dimethyldiphenoxygermane

Certain new poly(silyl ether)s and a poly(germyl ether) were synthesized by the polyaddition of bisepoxides with dimethyldiphenoxysilane (MPS) and dimethyldiphenoxygermane (MPG). The polyaddition of Bisphenol A diglycidyl ether (BPGE) with MPS proceeded very smoothly and regioselectively using quaternary onium salts such as tetrabutylammonium chloride (TBAC) and tetrabutylphosphonium chloride (TBPC) as catalysts at 100 °C to give the corresponding poly(silyl ether)s having high molecular weights, although the reaction did not occur without a catalyst under the same reaction conditions. The polyaddition also proceeded using either triphenylphosphine (TPP), triethylamine (TEA), or a complex of 18-crown-6 with potassium chloride as catalysts to give the poly(silyl ether)s, but with low molecular weights. The polyaddition of BPGE with MPG produced the corresponding poly(germyl ether) with good yield using TBAC as a catalyst; however, the molecular weight of the isolated poly(germyl ether) was lower than that of the obtained poly(silyl ether) under the same conditions.

Novel Syntheses of Poly(phosphonate)s and Poly(phosphate)s by Addition Reactions of Bisepoxides with Phosphonic Dichlorides and Dichlorophosphates

Poly(phosphonate)s and poly(phosphate)s with reactive pendant chloromethyl groups were synthesized by polyadditions of bisepoxides with phosphonic dichlorides and dichlorophosphates, respectively. The polyaddition of Bisphenol A diglydcidyl ether (BPGE) with phenylphosphonic dichloride (PPDC) occurred without any catalyst at 90°C for 24 h in toluene ; however, the yield and molecular weight of the resulting polymer were relatively low. On the other hand, the polyadditions of BPGE with PPDC proceeded very smoothly and regioselectively with high yields (90-96%) to give the polymers with relatively high molecular weights in toluene at 90°C for 24 h when quaternary ammonium or phosphonium salts were used as catalysts. The polyaddition was enhanced by the addition of triethylamine, triphenylphosphine, or crown ether complex ; however, the catalytic activities of these compounds were lower than those of quaternary onium salts. Polyadditions of bisepoxides such as BPGE and ethylene glycol diglycidyl ether with certain phosphonic dichlorides and dichlorophosphates also proceeded smoothly and regioselectively to give the corresponding polymers under the same reaction conditions.