Radiation-induced solid-state polymerization in binary systems. IV. Solid-state polymerization in the glassy phase

The radiation-induced polymerization of glass-forming systems containing monomers has been investigated. It was found that irradiation below the second-order transition temperature T_g of the systems causes no in-source polymerization but causes a rapid postpolymerization on warming above the T_g after initial irradiation below the T_g. The post-polymerization was followed by differential thermal analysis and ESR spectra. It is caused above the T_g by the release of peroxy radicals trapped below the T_g, and its rate is proportional to the irradiation dose to some extent, often is explosively high, and brings about a remarkably large temperature rise by accumulation of polymerization heat. Irradiation above the T_g causes rapid in-source polymerization which is accelerated by the high viscosity of the monomeric system between T_g and T_s (WLF temperature) compared to crystal or ordinary solution polymerization. The temperature dependence of the in-source polymerization of glassy systems shows a peak between the T_g and T_s which may be the result of competing effects of the rate increase by the decreased termination near T_s and the rate decrease by the decreased propagation caused by the diffusion prevented near the T_g. The degree of polymerization was also investigated. The temperature dependence of the degree of polymerization of the polymers obtained by in-source polymerization shows a peak similar to that of the temperature dependence of conversion. Unusually large values of the Huggins constant k' are noted between T_g and T_s. The degree of polymerization of the polymer obtained by post-polymerized increases with the increase of irradiation dose and the polymerization rate; this may be the result of decreased chain transfer to nonpolymerizable components.     

Vibration-rotation spectrum of formaldehyde: CH stretching fundamentals ν1 and ν5

The infrared vibration-rotation spectrum of formaldehyde vapor has been measured in the region from 2600 to 3400 cm^?1 with resolution from 0.04 to 0.07 cm^?1. An extensive rotational analysis of the ν₁ and ν₅ bands has confirmed and superseded the previous band-contour analysis of a medium-resolution spectrum. A large number of subbranches of both the ν₁ and ν₅ bands are perturbed by the combination bands ν₃ + ν₆, ν₂ + ν₄, and ν₂ + ν₆, whereas the Coriolis interaction between ν₁ and ν₅ is weak. The following effective rotational constants (in cm^?1) are obtained:

$\text{ν}{}_1\text{= 2782.49(1), A}{}_1\text{= 9.250(5), B}{}_1\text{= 1.2968(6), C}{}_1\text{= 1.1321(2)}$

,

$\text{ν}{}_0\text{= 2843.35(2), A}{}_0\text{= 9.224(2), B}{}_0\text{= 1.2936(2), C}{}_0\text{= 1.1303(1)}$

, where the number given in parentheses is three times the standard error in the last digit.     

Grafting on wool. II. Stress–strain behavior of grafted fiber in water

The stress–strain behavior and hysteresis properties of various grafted wool fibers were studied. Three distinct regions on the stress–strain curve and hysteresis properties characteristic of the native wool fiber remain substantially intact, even though a large amount of a rigid polymer occurs. It was suggested that the microfibril and the matrix nature in the native wool fiber exist in the grafted wool structures. The electron microscopic results were also supported. These results can be explained on the basis of Menefee's model that the longitudinal mechanical behavior is more directly controlled by a high modulus matrix.     

苯、乙烯和乙苯在HZSM－5及其负载Co，Zn的催化剂上的吸附和脱附行为

用ＴＰＤ（程序升温脱附）和ＴＰＳＲ（程序升温表面反应）技术研究了苯、乙烯和乙苯在ＨＺＳＭ－５及其负载Ｃｏ、Ｚｎ的催化剂上的吸附和脱附行为．结果表明，苯的ＴＰＤ峰皆为弥散的单峰．乙烯在ＨＺＳＭ－５及Ｚｎ／ＨＺＳＭ－５催化剂上发生二聚、歧化和芳构化反应，在Ｚｎ／ＨＺＳＭ－５上乙烯的二聚和歧化反应能力减弱，芳构化能力增强．苯和乙烯ＴＰＳＲ行为与吸附苯和乙烯的先后顺序有很大关系，主要产物是甲苯、乙苯和苯乙烯等．乙苯在各种催化剂上发生裂解和脱氢反应．结合活性评价结果，对苯和乙烯在催化剂上直接生成苯乙烯的途径进行了探讨．     

Synthesis of alpha,alpha-dibromo esters as precursors of ynolates

Aliphatic alpha,alpha-dibromo esters, precursors of ynolates, were synthesized via bromination of lithium alpha-bromo ester enolates with 1,2-dibromotetrafluoroethane in good yields. alpha-Trimethylsilyl-alpha,alpha-dibromo esters were synthesized via radical bromination.     

Growth and some properties of Sc2AlB6 crystal obtained from the solution in aluminum melt

Crystals of Sc₂AlB₆ were grown using scandium oxide and elemental boron as starting materials in a self-component aluminum solution under an argon atmosphere. The growth conditions for obtaining single crystals of relatively large size were investigated. Sc₂AlB₆ single crystals were obtained in the form of prisms extending in the b-axis direction. The largest Sc₂AlB₆ crystals prepared had maximum dimensions of about 0.4×0.4×4.2 mm³. The values of the Vickers microhardness and the electrical resistivity of Sc₂AlB₆ crystals are 12.7±0.8 GPa and 43±8 μΩ cm, respectively. The oxidation of Sc₂AlB₆ crystals starts at about 773°C, and the weight gain after TG determination is 12.9 mass% at 1200°C. The oxidation products of Sc₂AlB₆ crystals could not determined.     

Emission spectra of CH(A 2Δ) from methane in an argon flowing afterglow

The CH A ²ΔX²Π emission was observed in the flowing afterglow reaction of charged species of argon with CH₄. Energetic considerations show that metastable argon ions, Ar^+M(⁴D, ⁴F, ²F, ²G, are plausible candidates, although the contribution of Ar²⁺ cannot be completely excluded. The CH A ²ΔX²Π spectrum was analyzed; the ratio of vibrational populations for the υ′ = 0 and 1 states, P_vib(υ′ = 0), is estimated to be 0.56 ± 0.17, and the effective rotational temperatures are (3.0 ± 1.5) × 10³ and (1.7 ± 0.4) × 10³ K, respectively.     

Electron spin resonance study of poly-3,3-bis-(chloromethyl)oxetane irradiated with ultraviolet light

When poly-3,3-bis(chloromethyl)oxetane has been irradiated at ?196°C in a nitrogen atmosphere with ultraviolet light, a triplet spectrum is observed. After warming the sample, both a doublet and a singlet ESR spectra are observed. These spectra are attributed to and ? CH₂? O, respectively. The formation mechanism of these free radicals is discussed. It is concluded that the main process of radical formation is the dissociation of chemical bonds from the excited state of the polymer produced through the energy absorption by irregular groups acting as sensitizers. In the presence of oxygen, the radical yield at ?196°C is greater than that in nitrogen atmosphere. This is attributed to the extra absorption of light by the charge transfer complexes of polymers with oxygen molecules. It is also proposed that participation of a charge transfer complex in photooxidation of ether is important in the primary radical formation step. When a polymer sample irradiated in vacuum with ultraviolet light is treated at ?78°C for a few minutes in the presence of air, peroxy radicals form. This shows that oxygen molecules diffuse very easily into this polymer, even at this low temperature.     

Effect of salt concentration on the nanostructure of weak polyacid brush in the amphiphilic polymer monolayer at the air/water interface

The effect of salt concentration on the nanostructure of a spread monolayer of ionic amphiphilic diblock copolymer, (diethylsilacyclobutane)m-b-(methacrylic acid)n, at the air-water interface was directly investigated by in situ X-ray reflectivity and neutron reflectivity techniques. Previously, we had found that a poly(methacrylic acid) (PMAA) hydrophilic layer under the water was not in the form of a simple polyelectrolyte brush but consisted of a dense carpet upper layer and a diffuse brush lower layer when the hydrophilic chain was long enough. Here we observed this double layer formation in the monolayer in aqueous NaCl solution at a constant surface pressure. The effect of salt added to the subphase differed with the salt concentrations, that is, below or above 0.1 M. In the presence of NaCl up to 0.1 M, both the hydrophobic layer and brush layer thicknesses decreased. On the other hand, both of them increased in the presence of NaCl above 0.1 M. Also, the carpet layer thickness was almost constant independent of the salt concentration. In addition, the brush top roughness showed a maximum in the presence of 0.1 M NaCl. The increase of the charge number on the PMAA chain and the screening effect of the Coulomb interaction by added salt ions were considered to be responsible for these phenomena.     

ESR study on the photosensitized decomposition of polyethylene

Several aromatic compounds were added to low-density polyethylene to determine their effects on the photodegradation of polyethylene. It was shown that some aromatic compounds indeed sensitize the hydrogen abstraction of the allylic hydrogen of unsaturated groups contained in polyethylene as an improper bond. The mechanism of photosensitization was investigated by an ESR method. It was found that the higher photoexcited triplet state of an aromatic molecule produced by the biphotonic ultraviolet light absorption transfers its excess energy to the unsaturated bond to excite it, and the excited unsaturated group releases its allylic hydrogen atom, giving an allylic radical.