Preparation and characterization of novel cycloaliphatic epoxy resins, which are derived from octadienyl compounds, were studied. From a model peracetic acid epoxidation reaction using 2,7‐octadienyl acetate‐1, the structure of the liquid resins is estimated to be mainly terminal epoxides and some amount of inner epoxide depending on the epoxide content. The epoxy resins offer lower toxicity and lower vapor pressure. The reactivity of the resin with acid anhydrides is moderate but faster than that of traditional cyclohexane epoxide‐type resins and slower than that of the glycidyl ester‐type resins. This reactivity was also examined using model compounds. The heat deflection temperature of the hexahydro‐phthalic anhydride‐cured resins is shown to be directly proportional to the number of epoxy groups in the molecules. The flexural strength of the cured resins is nearly equivalent to that of the commercial resins, although the flexural elongation of the resins is larger than that of the rigid cyclohexane epoxide‐type resins. The thermal stability of the cured resins is comparable to typical rigid cycloaliphatic resins; furthermore, high water resistance of the cured resins is suggested to be attributed to the hydrophobic character of the C8 chain by cross‐linking. © 1993 John Wiley & Sons, Inc.

Stereospecific polymerization of vinyl alkyl ether was studied; various kinds of compounds, such as metal oxides, metal halides, metal oxyhalides, metal sulfate complexes and organometallic compounds‐Lewis acid complexes, being used at low temperature or room temperature. The relationship between the structures of catalysts and the stereoregularities of polymers is discussed, and it is found that tetrahedral compounds which have one active edge are especially useful for making the stereoregular polymers at room temperature. Also, the shorter the length of active edge, the more suitable the catalyst is for stereospecific polymerization. On the basis of these experimental results, a mechanism of stereospecific polymerization of vinyl alkyl ether is proposed.

Cocatalytic reactivities of molecular oxygen and some oxygen compounds toward the organoboron‐induced vinyl polymerization were examined in detail. The oxygen compounds in an appropriate quantity accelerated the polymerization markedly, but these compounds in excess retarded the polymerization. The reactivity of the organoborm compounds examined decreased in the order: (n‐C4H9)2BOB(n‐C4H9)2 > B(n‐C4H9)3 > (n‐C4H9)2B(O‐n‐C4H9) > (n‐C4H9)2BBr > (n‐C4H9)2BCl. Triphenylboron, which was not inflammable in air, had a much smaller catalytic activity than the aliphatic boron derivatives. Copolymerizations of styrene‐methyl methacrylate and of styrene‐vinyl acetate with boron alkyl as catalyst resulted in the formation of copolymers having the same composition as those the typical radical copolymerization. This suggests a radical mechanism for the present polymerization where redicals arising from the reaction between organoboron and oxygen compound may induce the polymerization. Some features of these polymerizations were described in connection with chain transfer and chain termination with the organoboron compounds.

The copolymerizations of N‐vinylsuccinimide (VSI) and of N,N‐methyl vinyl p‐toluenesulfonamide (VSA) with vinyl acetate (VAc), acrylonitrile (AN), stryrene (St), methyl acrylate (MA), methyl methacrylate (MMA), and n‐butyl vinyl ether (BVE) were examianed at 60°C., using benzoyl peroxide or azobisiobutyronitrile as initiator. The monomer reactivity ratios and the monomer reactivity factors of VSI and VSA were as follows. VSI as monomer 1: r1 = 15, r2 = 0 (VBE); r1 = 0.09, r2 = 7.0 (St); r1 = 6.05, r2 = 0.185 (VAc); r1 = 0.4. r2 = 1.2 (MA); r1 = 0.16, r2 = 0.54 (AAAN), Q1 = 0.15, e1M/s = ‐0.26. VSA as monomer 1: r1 = 0, r2 = 0.42 (AN); r1 = 0, r2 = 4.68 (MMA) r1 = 0, r2 = 12.3 (St); Q1 = 0.092, e2 = ‐0.87. The difference in copolymeizability between VSI and VSA sesms to arise primarily from the difference in thieir polarity factors.

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