Polymerization of lactams, 55. Cyclic dimer of 6-caprolactam and its polymerization

Polymerization of the cyclic dimer of 6-caprolactam was investigated in N-methyl-2-pyrroli-done solution at 260°C under initiation with 6-aminocaproic acid or anhydrous phosphoric acid on the one hand, and in the solid phase at 230, 260, and 280°C in the absence of any other component or under initiation with anhydrous phosphoric acid, on the other. Monomeric 6-caprolactam was formed in all cases already at the beginning of reaction. It has been suggested that, in addition to the direct incorporation of the cyclic dimer into a polymer chain, the dimer is alos incorporated via the monomer, which is formed from the dimer by an intermolecular transamidation reaction.     

Polymerization of vinyl monomers photoinitiated by benzoylated polystyrene

The rate of the polymerization of vinyl monomers photoinitiated (at λ = 365 nm) by benzoylated polystyrene in N,N-dimethylformamide (DMF) decreases in the sequence vinyl acetate>acrylonitrile>methyl methacrylate ? styrene ≈ 0 and is related to the rate constant of propagation of the mentioned monomers. In addition to DMF, aromatic hydrocarbons (benzene, toluene, p-xylene), cyclohexane and tetrahydrofuran were employed as hydrogen donors. The maximum polymerization rate was achieved in the system containing p-xylene; the system with benzene turned out inefficient for the initiation of acrylonitrile polymerization. Turbidimetric titration of a soluble fraction of the acrylonitrile polymerization in DMF in presence of benzoylated polystyrene showed that the soluble fraction does not contain graft copolymers of benzoylated polystyrene with acrylonitrile. It is assumed, however, that the polyacrylonitrile in the insoluble fraction is bound to benzoylated polystyrene in the form of graft copolymers.     

Über die Wechselwirkung des Katalysators und Cokatalysators mit dem Monomeren und dem Polymeren bei der kationischen Polymerisation des Isobutylens. II. Modellstudium des Polymerisations-Depolymerisations-Gleichgewichts im System Triisobutylen/AlBr3/DBr/Heptan

In the reaction of triisobutylene with AlBr₃/DBr system, backbone isomerization and formation of higher oligomers takes place, in addition to deuteration. Both reactions are explained by the cleavage of the backbone bonds of the intermediate carbonium ions. The fragments formed can react with other components of the reaction system. The possible role of these reactions in the mechanism of termination and chain transfer in the cationic polymerization of isobutylene is discussed briefly.     

Infrared spectra and sequence length distribution in free radical styrene/methacrolein copolymers

The method of azoisobutyronitrile (AIBN)-initiated bulk copolymerization of styrene (S) and methacrolein (M) was employed to determine the monomer reactivity ratios r_S = 0.15 and r_M = 0.55 (Q_M = 1.50, e_M = 0.78). Quantitative IR spectroscopy in the region of 4000–450 cm^?1 was used to elucidate the structure of copolymers. In addition to methacrolein units containing aldehyde groups, the copolymers may also contain cyclic hemiacetal structures formed by the reaction of the carbonyls of the neighboring methacrolein units. The carbonyl absorption at 1722 cm^?1 showed that, up to 30 mole-% methacrolein in the copolymer, almost all methacrolein units have free aldehyde groups. The number of cyclic structures increases with the concentration of methacrolein in the copolymer. The experimental data are in agreement with the statistical theory on the sequence length distribution. The shift of the styrene band at 540 cm^?1 to higher wavenumber was investigated and related to the shortening of sequence length of the styrene units. The intensity of the styrene band at 760 cm^?1 was related with the distribution of the MSM triads and the copolymer structure.     

Serum progesterone at the time of human chorionic gonadotrophin does not predict pregnancy in in-vitro fertilization and embryo transfer

Controversy exists as to whether the serum concentration ofprogesterone on the day of human chorionic gonadotrophin (HCG)administration following ovarian stimulation for in-vitro fertilization(IVF) and embryo transfer can be used to predict the likelihoodof success. This retrospective study was undertaken to answerthis question by analysing a large population of IVF and embryotransfer cycles (n = 756). In addition to the concentrationof progesterone on the day of HCG administration, all variablesknown to impact on IVF and embryo transfer success (such aspatient age), indication for IVF and embryo transfer, numberof oocytes retrieved and the number of embryos generated andtransferred were examined. There was a significant increasein the number of oocytes retrieved with increasing progesteroneconcentration at the time of HCG administration. However, therewas no correlation of progesterone concentration at HCG administrationwith pregnancy and implantation rates. It is concluded thatprevious reports associating a slight elevation of progesteronein gonadotrophin- releasing hormone agonist ovarian stimulationcycles for IVF and embryo transfer may be misleading becauseof a small sample size or the presence of confounding variablesthat affect IVF and embryo transfer success.     

Shb null allele is inherited with a transmission ratio distortion and causes reduced viability in utero.

SHB is an Src homology 2 domain-containing adapter protein that has been found to be involved in numerous cellular responses. We have generated an Shb knockout mouse. No Shb-/- pups or embryos were obtained on the C57Bl6 background, indicating an early defect as a consequence of Shb- gene inactivation on this genetic background. Breeding heterozygotes for Shb gene inactivation (Shb+/-) on a mixed genetic background (FVB/C57Bl6/129Sv) reveals a distorted transmission ratio of the null allele with reduced numbers of Shb+/+ and Shb-/- animals, but increased number of Shb+/- animals. The Shb- allele is associated with various forms of malformations, explaining the relative reduction in the number of Shb-/- offspring. Shb-/- animals that were born were viable, fertile, and showed no obvious defects. However, Shb+/- female mice ovulated preferentially Shb- oocytes explaining the reduced frequency of Shb+/+ mice. Our study suggests a role of SHB during reproduction and development.     

Radical reactions initiated by chelate complexes of transition metals, 12. Decomposition of cumene hydroperoxide by the system copper acetate-aminoalcohol

This paper presents an investigation of the kinetics of the decomposition of cumene hydroperoxide (1-methyl-1-phenylethyl hydroperoxide) (CHP) in benzene/methanol (95:5, by vol.) in the presence of copper(II) acetate (A) and different aminoalcohols (L), such as 2-aminoethanol, 2-(2-hydroxyethylamino)ethanol, 2-[bis(2-hydroxyethyl)amino]ethanol, 1-amino-2-propanol, and 2-(diethylamino)ethanol. It has been found that the decomposition of CHP takes place via a complex formed from the components of the reaction system. The individual components of the catalytic system (i. e. A or L), when applied separately, do not contribute to an acceleration of the decomposition reaction. Under the given conditions the initial rate of the CHP decomposition v_o is expressed formally by the equation where [A₂]₀, [L]₀, and [CHP]₀ are the initial concentrations of the above mentioned compounds; k is the monomolecular rate constant for the decomposition of the complex between metal compound and CHP, and K_L, K_c and K_A are the equilibrium constants for the formation of the adduct from aminoalcohol and copper(II) acetate, the formation of the complex consisting of this adduct and CHP and for the dimerisation of copper(II) acetate, resp.     

On the interaction of styrene-maleic anhydride copolymer with styrene

The interaction between alternating styrene/maleic anhydride copolymer as polymeric acceptor and styrene as low molecular weight donor in acetone and/or tetrahydrofuran was investigated by UV spectroscopy and polymerization technique. The equilibrium constant for the complex formation between styrene and the maleic anhydride structural unit of the styrene/maleic anhydride copolymer at 20°C was found to be 0,02 ± 0,001 dm³·mol^?1 in acetone and 0,06 ± 0,003 dm³·mol^?1 in tetrahydrofuran. The results of the thermally initiated polymerization of styrene in acetone in the presence of the alternating styrene/maleic anhydride copolymer indicate that the copolymer or the products of the interaction between the monomeric units of maleic anhydride in the copolymer and styrene do not initiate a radical polymerization of styrene.