Polymerization of 1,3‐dienes with functional groups. III. Free‐radical polymerization of N,N‐diethyl‐2‐methylene‐3‐butenamide

Free‐radical homo‐ and copolymerization behavior of N,N‐diethyl‐2‐methylene‐3‐butenamide (DEA) was investigated. When the monomer was heated in bulk at 60 °C for 25 h without initiator, rubbery, solid gel was formed by the thermal polymerization. No such reaction was observed when the polymerization was carried out in 2 mol/L of benzene solution with with 1 mol % of azobisisobutyronitrile (AIBN) as an initiator. The polymerization rate (R_p) equation was R_p ∝ [DEA]^1.1[AIBN]^0.51, and the overall activation energy of polymerization was calculated 84.1 kJ/mol. The microstructure of the resulting polymer was exclusively a 1,4‐structure where both 1,4‐E and 1,4‐Z structures were included. From the product analysis of the telomerization with tert‐butylmercaptan as a telogen, the modes of monomer addition were estimated to be both 1,4‐ and 4,1‐addition. The copolymerizations of this monomer with styrene and/or chloroprene as comonomers were also carried out in benzene solution at 60 °C. In the copolymerization with styrene, the monomer reactivity ratios obtained were r₁ = 5.83 and r₂ = 0.05, and the Q and e values were Q = 8.4 and e = 0.33, respectively. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 999–1007, 2004     

Changes in the near-edge X-ray absorption fine structure spectra of long-chain diacetylene derivatives through photopolymerization in Langmuir–Blodgett films

Photopolymerization of cadmium 10,12-pentacosadiynoate (CdDA) in Langmuir–Blodgett (LB) films, with the molecular packing well arranged by moderate preannealing, was investigated with near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. Greenish films of polydiacetylene with an absorption wavelength of 705 nm were obtained through the photopolymerization of preannealed monomer LB films, and this resulted in an extended π-conjugate system based on the well-ordered monomer in a two-dimensional arrangement. The electronic structures of the polydiacetylenes were found to be correlated to the variation of the molecular arrangements in the films from the changes in the NEXAFS spectra through photopolymerization in the LB films. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2329–2336, 2004     

Application of total reflection X-ray fluorescence spectrometry to small glass fragments.

Total reflection X-ray fluorescence spectrometry (TXRF) has been applied for trace elemental analysis of small glass fragments. A small glass sample (a fragment with weight less than 0.5 mg) was decomposed by 100 microg of HF/HNO3 acid; the material was condensed to 10 microl and was dried on a Si wafer. Since the size of the dried residue on the Si wafer was less than 1 cm in diameter, an incident X-ray beam with about 1 cm in width could effectively excite elemental components in such a small glass fragment. The precision of the present technique was checked by analyzing the glass fragments (<0.5 mg) from NIST SRM612; the relative standard deviations (RSD) of less than 8.1% were achieved for elemental ratios that were normalized by Sr. Fragments (<0.5 mg) obtained from 23 figured sheet glasses were used as samples for estimating the utility of this technique to forensic discrimination. Comparison of five elemental ratios of Ti/Sr, Mn/Sr, Zn/Sr, Rb/Sr, and Pb/Sr calculated from X-ray fluorescence spectra was effective in distinguishing glass fragments that could not be differentiated by their refractive indexes (RI).     

Numerical analysis of finite amplitude motion of waves and a moored floating body under severe storm conditions

The motion of a moored floating body under the action of wave forces, which is influenced by fluid forces, shape of the floating body and mooring forces, should be analysed as a complex coupled motion system. Especially under severe storm conditions or resonant motion of the floating body it is necessary to consider finite amplitude motions of the waves, the floating body and the mooring lines as well as non-linear interactions of these finite amplitude motions. The problem of a floating body has been studied on the basis of linear wave theory by many researchers. However, the finite amplitude motion under a correlated motion system has rarely been taken into account. This paper presents a numerical method for calculating the finite amplitude motion when a floating body is moored by non-linear mooring lines such as chains and cables under severe storm conditions.     

Determination of arsenic at the picogram level by atomic absorption spectrometry with miniaturized suction-flow hydride generation

A continuous-flow hydride generator is modified and miniaturized for the determination of picogram amounts of arsenic by atomic absorption spectrometry. A 300-μl sample is dropped into a teflon cup and pumped into an alkaline sodium tetrahydroborate stream, which is acidified in a reaction coil. The evolved hydride is swept with argon through a phase separator into an electrically-heated quartz absorption cell and the absorbance is recorded. To eliminate differences in sensitivity between arsenic(III) and arsenic(V) without prereduction by potassium iodide, it is important that arsenic(V) be mixed with tetrahydroborate prior to mixing with hydrochloric acid. The method has a detection limit of 0.08 ng As ml^?1 (24 pg) and the calibrations is linear up to 50 ng As ml^?1. The relative standard deviation for 10 replicate measurements is 5.4% for 0.5 ng As ml^?1. The addition of potassium iodide and hydroxylamine is confirmed to be effective in minimizing some interferences. The sampling rate is 90 h^?1. Results for NBS biological and steel reference materials demonstrate applicability of the technique.     

Kinetic approach to radiation-induced grafting in the polyethylene–styrene system. II

The investigation method reported in the previous paper was applied to four reaction methods: preirradiation method with reaction in liquid monomer, preirradiation method with reaction in monomer vapor, simultaneous irradiation method in liquid, and simultaneous irradiation method in vapor. The increasing patterns and values of the degree of grafting experimentally obtained roughly agreed with those calculated by using the same rate constants. At high monomer concentration, the rate of grafting was small; at low monomer concentration, the rate of grafting was large. Strictly speaking, the data by simultaneous irradiation method were somewhat larger than those by calculation. Two additional factors, as homopolymerization and the grafting from the radicals formed on the grafted polystyrene, were considered and discussed. The rate constants obtained were also discussed.     

Preparation and synthetic application of methyl β,β-difluoro-α-trimethylsilyloxyacrylate: a fluoride ion-promoted desilylative-defluorination route

Catalytic amount of TBAT (0.2 mol %) promoted desilylation and subsequent defluorination of ketene silyl acetal of methyl O-trimethylsilyltrifluorolactate, affording methyl β,β-difluoro-α-trimethylsilyloxyacrylate in 95% yield of which reaction with electrophiles provided methyl β-substituted-β,β-difluoropyruvate in good yields.     

Charge-order pattern of the low-temperature phase from a monoclinic single domain of NaV2O5 uniquely determined by resonant x-ray scattering

The present resonant x-ray scattering has been performed on a monoclinically split single domain of NaV(2)O(5). The observation of a critically enhanced contrast between V(4+) and V(5+) ions has led us to the unequivocal conclusion of the charge-order pattern of the low-temperature phase of NaV(2)O(5) below T(c) = 35 K. In spite of the possible four types of configuration of the zigzag-type charge-order patterns in the ab plane (A,A',B and B'), the stacking sequence along the c axis is determined as the AAA'A' type by comparison with model calculations.     

Charge transport study on single crystals of β-LiAl

Charge transport properties of β-LiAl were studied in the composition range of 48.0–50.2 at.% Li. Measurements were made on single crystal samples and down to the liquid He temperature. The resistivity changes linearly with temperature above 125 K, with a thermal coefficient of 72–95nΩ cm K^?1. The Matthiessen law was obeyed very well. A component dependent on temperature, which was described by the Grüneisen formula, is insensitive to a change of the chemical composition. On the other hand, the residual resistivity depends largely on the composition and contributes up to 58% of the total resistivity in Li_0.498. It is chiefly due to the substituted Li atoms on the Al sublattice.