Study of photopolymer. XVII. Synthesis of novel photosensitive polymers with pendant photosensitive group and photosensitizer groups

Novel photosensitive polymers with pendant photosensitive group, such as cinnamic ester, and photosensitizer groups, such as N-carbamoyl-p-nitroaniline and N-carbamoly-4-nitro-1-naphthylamine, were synthesized from radical copolymerizations of (2-cinnamoyloxy)ethylmethacrylate with photosensitizer monomers, such as p-nitrophenylmethacrylamide and 4-nitro-1-na-phthylmethacrylamide, by using asobisisobutyronitrile (AIBN) in benzene and from the copolymerizations of (2-hydroxy)ethylmethacrylate or (2-hydroxy)ethylacrylate with photosensitizer monomers by using AIBN in DMF. This procedure was followed by condensation reactions of the copolymers with cinnamoyl chloride with pyridine as HCL acceptor in the same reaction flask. The photoreactivities of the polymers obtained were influenced by the concentration of photosensitive group and photosensitizer groups and their ratio in the polymer matrix. In addition, the photosensitivity of cinnamic ester groups attached to a soft polymer segment was higher than that of cinnamic ester group attached to a hard polymer segment when these polymers had the same pendant N-carbamoyl-p-nitroaniline group as photosensitizer. Furthermore, the spacer length between the polymer chain and photosensitizer group was important for increasing the photoreactivity of the photosensitive group in the polymers with pendant cinnamic ester and N-carbamoyl-p-nitroaniline groups.     

On a first-passage problem for a cumulative process with exponential decay

A first-passage problem for a cumulative process is investigated. The cumulative process is assumed to be generated by a Poisson process, and the amplitude generated by an event is assumed to decay exponentially. An integral equation for the probability density of the first-passage time until the total amplitude exceeds a pre-specified threshold level is derived. The Laplace transform of the probability density of the first-passage time is obtained explicity when each amplitude generated by an event is distributed exponentially. The mean first-passage times are given in a closed form and plotted versus the threshold level.     

Chemical reactivities of the cation and anion of M@C82 (M = Y, La, and Ce)

The chemical reduction and oxidation of M@C82 (M = Y, La, and Ce) afford the corresponding anion and cation, respectively, which show unique and interesting chemical reactivities. It is found that the successful reversible gain or loss of electrons by ionization is useful for controlling the stability and reactivity of M@C82 toward both nucleophiles and electrophiles.     

Purely periodic -expansions with Pisot unit base

Let 1$"> be a Pisot unit. A family of sets defined by a -numeration system has been extensively studied as an atomic surface or Rauzy fractal. For the purpose of constructing a Markov partition, a domain constructed by an atomic surface has appeared in several papers. In this paper we show that the domain completely characterizes the set of purely periodic -expansions.

     

General description of mechanical anisotropy of semicrystalline polymers in relation to orientation of structural units composed of crystalline and noncrystalline materials

A mathematical representation of the transformation of an orientation function between two sets of Cartesian coordinates is discussed in terms of a series expansion of the distribution function in generalized spherical harmonics. A general procedure for calculating the mechanical anisotropy of a single-phase system (a polycrystalline material) from the orientation of its structural units and the intrinsic mechanical anisotropy of the structural unit is discussed in relation to the transformation of the orientation distribution function, i.e., mutual conversion of the coefficients in the expansion of the distribution function between the two sets of Cartesian coordinates. The procedure is extended to a two-phase systems (semicrystalline polymers) containing structural units composed of crystalline and noncrystalline materials in three different geometrical arrangements.     

X-ray photoelectron spectra of ylide—TCNQ charge-transfer complexes

Charge-transfer complexes of TCNQ with ylides, new-type donors, were synthesized and the X-ray photoelectron spectra of these complexes were measured. A broad satellite caused by TCNQ radicals observed.     

Selective extraction and purification of endohedral metallofullerene from carbon soot

A preferential extraction of endohedral metallofullerenes (EMFs) from carbon soot through the use of reduction in the extraction process and a convenient isolation of endohedral metallofullerene anions (EMFs(-)) and empty fullerenes utilizing their difference in solubility are accomplished. EMFs are easily isolated by one-stage high-performance liquid chromatography after chemical oxidation of the extracted endohedral EMFs(-).