High‐molecular‐weight branched‐addition polymers made from oligomeric solid epoxy resins and amines carrying two active hydrogen atoms are described. The reaction with aliphatic amines like ethanolamine, 2‐ethylhexylamine, or piperazine can easily be controlled carrying out the polymerization in about 15% solutions of boiling 2‐methoxyethanol. Less basic derivatives of aniline and epoxy resins are processed at 200°C in the molten state. Polymers with Mn up to 33,000 and Mw to 720,000 are obtained. Properties of films and injection moldings are described. The tertiary nitrogen atoms present in the polymer chain can be quaternized with alkylating agents, like dimethylsulfate, methyliodide, or trimethyl phosphate. Thin membranes cast from the polyquats thus obtained exhibit a good flow rate for water and a high salt rejection under reverse osmosis conditions.

SynopsisThe cyanoacetamides NC-CHp-CO-NH-RI-N (&) ( R3) are a new family of accelerators for the epoxy /isocyanate ( E P /IC ) reaction. Results obtained from systematic structure variations indicate that they belong to the "deactivated tertiary amine" type of catalyst with the cyanoacetamide group as the deactivating moiety. Reactivity can be controlled via the R1 substituent (cyanoacetamide) and/or by &/R3. A reaction mechanism is proposed. The results of a factorial design experiment and IR determination of the oxazolidinone (OX)/isocyanurate (ICR) extinction maxima ratios were used to develope an optimized EP/IC system. A trial formulation (filled) is given in which rapid gelation, a high T8 value, and excellent mechanical properties were achieved with an accelerator concentration of less than 0.2%.

Cyanoacetamides are a novel class of curing agents for epoxy resins. Since reaction products of epoxy compounds with cyanoacetamides have not yet been described, we investigated the reaction of phenyl‐glycidylether (PGE) and N‐isobutylcyanoacetamide (NICA) under the conditions of the epoxy cure (120–150°C). Twenty‐two fractions of the reaction product have been separated by preparative TLC and characterized by FD and MS mass spectroscopy. The structures of 10 reaction product have been elucidated by MS, NMR, and IR techniques. They belong to the classes of cyclic urethanes, spiro‐dilactones, cyclo‐oxa‐1‐hepten‐4‐one‐2, pyrimidones, aminocrotononitrile, and tertiary amine. This complex model reaction mixture does not enable us to propose a curing mechanism. However practical cure of Bisphenol A diglycidylether (BADGE) yields clear and tough solids with a glass transition temperature up to 200°C, good mechanical strength, and high adhesion to metal surface. Cyanoacetamides are latent hardeners requiring a curing initiator. Since N‐4‐chlorophenyl‐N′‐dimethylurea is a latent initiator, liquid, homogeneous, storage stable “one shot” systems can be formulated which harden quickly above 120°C. Heat aging properties of cured specimens are reported. A series of novel liquid, resinous, and crystalline cyanoacetamides and their potential as curing agent are described.

SynopsisSolid ketone-formaldehyde resins are used in certain coating formulations in order to improve hardness, gloss, and light stability. They are soluble, thermoplastic by nature, and contain limited amounts of hydroxyl groups. We found that their primary hydroxyls can be etherified with epichlorohydrin (ECH) either by a two-step ECH-addition/dehy&ohalogenation procedure or by a one-step phase-transfer process. An intermediate of particular usefulness is the crystalline 2,2,6,6-tetramethylol-cyclohexanol (TMCH) made from cyclohexanone and 5 mol formaldehyde, yielding low colored epoxy resins with epoxy values up to 7.5 eq/kg. Depending upon the nature of the curing agent, high Tp solids as well as tough and flexible coatings with good outdoor stability can be made. Upon decreasing the formaldehyde-cyclohexanone ratio, solid condensation polymers melting up to 150°C can be obtained. Phase-transfer glycidylation yielded solid thermoset glycidyl ether resins with a,, up to 1600, up to 13,000, epoxy values up to 3.6 eq/kg, and softening points between 80 and 160°C. Powder coatings formulated with carboxyterminated polyesters are hard, glossy, solvent-resistant but somewhat brittle. In order to overcome this drawback, polycycloacetals have been produced from TMCH and glutardialdehyde, which are terminated by pairs of methylol groups. Powder coatings of the corresponding glycidylethers with carboxyl-terminated polyesters exhibited excellent flexibility and impact strength.

SynopsisAllyl-bicyclo-(2,2,1)hept-5-en-dicarboxylic(2,3)imides (allylnadic-imides) are prepared by heating equivalent amounts of allylnadic anhydride and amines. Mixtures of isomers (1-allyl-endo, 6-allyl-endo and exo) were obtained, separated by flash chromatography and identified by 'Hand 13C-NMR. A series of novel allylnadic-imide monomers is described. Upon heating to 250°C oligomers are obtained. Diels-Aider rearrangement and "ene" type addition reactions seem to play a major role in oligomer formation. Bisand tris-allylnadic-imides are viscous liquids resins or low melting solids, which are soluble in common solvents. Upon heating to 250°C insoluble, high TB solids are obtained with good thermooxidative and environmental stability and with reduced burning rate. Cured allylnadic-imide resins are excellent high temperature insulators and low permittivity dielectrics. Crosslinked copolymers with maleic-imides and epoxy resins are described. Neat resin and carbon fiber composite properties are reported.by the thermal polymerization of allylnadic anhydride.2 Solid, soluble polyan- Preparation of endo-1-Allylnadic-N-isobutylimide (6a) andendo-6-Allylnadic-N-isobutylimide (6b, see below)In a 250 mL flask equipped with a stirrer, condenser, and a Dean-Stark trap is placed 20.4 g (0.11 mol) of allylnadic anhydride, 8 g (0.11 mol) of distilled isobutylamine, and 100 mL toluene. The apparatus is purged with