Dynamic mechanical properties of polycarbonate and its derivatives were measnred over temperature range from -130°C to the glass transition temperatures. It is considered that the α dispersion is associated with the micro Brownian motion in the main chains, theβ dispersion associated with the motion of molecular chains in the regions of weak intermolecular bonds, and the γ dispersion associated with the carbonate groups in the main chains.
Polycarbonates containing halogen atoms have a new broad and large dispersion different from the β dispersion of bis-phenol A polycarbonate. It is supposed that the dipole-dipole association between the halogen atoms contributes to this dispersion. In addition the γdispersion disappears by introducing halogen atoms in the benzene ring. The γ dispersion of 4, 4'-dioxy diphenyl-2, 2-butane polycarbonate shifts to lower temperature because of the bulky branched group.

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The heat of fusion of a crosslink of gels (ΔH), the color reaction of iodine (D₅₈₄) and mechanical denaturability of two kinds of poly (vinyl alcohol)(PVA) were studied. The PVA (TMS- and VAc-PVA) derived from poly (vinyl trimethylsilylether) prepared by cationic polymerization at low temperatures and that derived from poly (vinyl acetate) prepared by photo-sensitized polymerization at the temperatures below about 30°C were used.
The values of ΔH were 8-10kcal/mol and about 10kcal/mol for TMS-PVA and VAc-PVA respectively. These are higher than that of commercial PVA.
Percentages of syndiotactic diads (s-(diad)%) of TMS-PVA and VAc-PVA were nearly equal to that of commercial PVA. Absorbance D584 and mechanical denaturability of TMS-PVA and VAc-PVA were higher than those of commercial PVA, although ΔH, sdiad % D₅₈₄ and the yield of coagulations by shear of TMS-PVA and VAc-PVA were smaller than those of the PVA derived from poly (vinyl trifluoroacetate).
These results suggest that the sequence length of syndiotactic part of TMS-PVA and VAc-PVA is longer than that of the PVA derived from poly (vinyl acetate) prepared by catalytic bulk polymerization at 60°C and that the length influences the mechanical denaturation.

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The dimensional change of polymer spherulite during uniaxial stretching and after releasing the bulk specimen was invesigated by means of light-scattering technique by using three kinds of polyethylenes, which gave spherulitic specimens having several microns spherulites in diameter as test polymers.
After calculations from Samuels' and Moore's equations, it was found that the spherulites in the spherulitic speimens deformed in the affine fashion while keeping their volumes constant during stretching the bulk specimen upto 50%-elongation and after releasing from the %-elongations.
The light-scattering patterns as undeformed state as well as deformed state from the specimens of the three kinds of polyethylenes differed considerably from each other, in spite of almost same density and degree of crystallinity ranked as medium density polyethylene, which may be reflected from the difference of fine structure between the spherulites.

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Summary The possibility of evaluating the second virial coefficient for dilute solution by use of vapor pressure osmometry was studied on the basis of the steady state theory established in the previous paper (K. Kamide et al.: The Chemistry of High Polymers, Japan 24, 751 (1967)). Except for the case where heat transfer other than condensation could be completely ignored, the apparent second virial coefficint A “_{2, v}obtained from concentration dependency of steady state values of temperature difference does not generally agree with the second virial coefficient A_{2, o} derived from the osmometry, but there holds a relation between A” _{2, v}and A_{2, o}, as shown below:
_??_
where
_??_
V₀: molar volume of solvent, M₁: molecular weight of solute, ΔH: heat of condensation of solvent vapor, R: gas constant, T₀: temperature of solvent drop, k₁and k₂: coefficients of heat transfer at the interfaces between vapor-solution and between solution-ther-mistor, respectively, k₃: coefficient of material transfer between vapor-solution, A₁: surface area of solution drop, A₂: surface area of thermistor in contact with solution. When the molecular weight of solute is up to 104, the third term on the right-hand-side of the above formula is larger than or equal to A_{2, o}. If the apparent second virial coefficient A “_{2, v} is evaluated by ignoring concentration changes caused by condensation of solvent and by approximating steady state concentration with initial one, the result does not agree with true A” _{2, v} so far as the molecular weight of solute is smaller than 104. In practice, heat transfer other than condensation is by no means ignorable, and the maximal measurable molecular weight through the vapor pressure osmometry is about 104. Accordingly, it is actually impossible to appreciate A_{2, o} exactly by use of the latter method. On the other hand, solvent activity in solution can be determined exactly through the vapor pressure osmometry.
The theoretical prediction given in the above was ascertained by the experimental results for benzene solution of m-terphenyl and by the values for other solutions of low molecular weight compounds found in the literature.

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The co-condensation reaction when phenol was added to acetoguanamine-formaldehyde resin (AGR) was studied. One is the non-catalytic curing reaction i) and the other is the reaction in the mixed solvent of dioxane-water, using hydrochloric acid as a catalyst ii).
By assuming that co-condensation reaction is caused mainly by the following two condensation reactions and phenol is bifunctional,

_??_
(I)
_??_
(II) the behavior of the reaction of i) and ii) was investigated by the mathematical treatment of the results of kinetics experiments.
In the case of i), it was found that the competitive reaction could be neglected from the analysis of the products and kinetic data that the methylol group -CH₂OH in AGR reacted predominantly with phenol (II) and only slightly with the amino group-NH₂ (I). In the case of ii), it was also recognized from kinetic data that two condensation reactions of the methylol group with the amino group in AGR (I) and with phenol (II) occured simultaneously and the value of the ratio k₁/k₂ was about 1. 5.
In both cases of above reactions, phenol, appeared to have character than be trifunctional, the decrease in the concentration of phenol was found to be in reasonable harmony with a second-order reaction equation.

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In the thermal reaction of polyvinyl chloride (PVC) with di-n-butyltin (DBT) or di-nbutyltin dihydride (DBTH), the structures of decomposed PVC and of reacted organotin compounds were investigated. The principal results were as follows:
In a solution system using tetrahydrofuran, as a solvent Sn contents in the decomposed PVC reached 0.87% and 1.42% respectively, on the reactions of PVC with DBTH at 140°C and with DBT at 160. By using triethylamine as a catalyst, Sn contents reached 3.92% and 3.30% respectively, on the similar reactions with DBTH with 165°C and with DBT at 160°C.
It was suggested that trialkyltin chloride (Bu₂RSnCl, R: PVC residue) and tetraalkyltin (Bu₂R₂Sn) were formed in the decomposed PVC.
Chlorine in PVC was partially replaced with hydrogen by DBTH in a solution or in a solvent-free system. In the former system, the rate of reduction was affected by solvents, In the latter system, characteristic depolymerized products (molecular weight: e. g. 960) were formed, which were presumed to be hydrocarbons containing unsaturated structures-(CH=CH)_n-(n=1, 2, 3).

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The preparation of stereoregular poly (vinyl alcohol) via a cationic polymerization of vinyl trimethylsilyl ether was reported previously. In this paper an application of the same synthetic principle to the synthesis of poly (isopropenyl alcohol) and poly (propenyl alcohol) is described._??_
Monomers are isopropenyl trimethylsilyl ether (ITE) and propenyl trimethylsilyl ether (PTE) and were prepared according to Nesmeyanov's and Petrov's method, respectively. The polymerization was carried out at -78°C using Friedel-Crafts catalysts. Poly (isopropenyl alcohol)(PIA) was found to be unstable in acidic solutions, so that it was necessary to carry out the solvolysis of poly (ITE) under basic conditions. Poly (propenyl alcohol)(PPA), on the other hand, is stable in acidic solutions and solvolysis of poly (PTE) was done by acidic methanol.
Complete cleavage of the O-Si bond was confirmed by elemental analysis and IR spectroscopy. The molecular weight of the resulting polyalcohols were very low (ηsp/C=0.04-0.06dl/g at 30°C on 1% methanol solutions).

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Several copolymers of maleic acid (MaA) were prepared by hydrolysis of alternative copolymers of maleic anhydride. These copolymers were MaA-vinyl acetate (A), -vinyl alcohol (B), -isopropenyl acetate (C), -isopropenyl alcohol (D), -allyl acetate (E), -allyl alcohol (F) and-vinyl succinimide (G). Further, MaA-vinyl acetate (A') and MaA-vinyl alcohol (B') were derived from the alternative copolymer of diethyl fumarate and vinyl acetate. Lactonization of B, B', D and F, acid anhydride formation of A, A', C, E and G, potentiometric titration of A, A', B', C, E and F were investigated. These behaviors of the polymers were remarkably different from each other, and such results could be explained mainly by difference of the spacial distance between neighbored side chains in the polymer molecule.

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Formation of acid anhydride of various polymeric carboxylic acids was examined. As the polymers were used alternative copolymers of maleic anhydride and nonionizable comonomers such as vinyl acetate, vinyl benzoate, vinyl pyrrolidone, methyl acrylate, methyl methacrylate and styrene, the hydrolysis product of the alternative copolymer of diethyl fumarate and styrene, atactic polymers of monocarboxylic acids such as acrylic acids, methacrylic acid, crotonic acid, vinyl acetic acid, p-vinyl benzoic acid and atropic acid, and atactic polymers of dicarboxylic acids such as maleic anhydride, citraconic acid and itaconic acid. In general, acid anhydride rings of five members could be more easily formed than those of six members. With the exception of some polymers, the polymers which are considered to contain neighbored carboxyl groups with shorter spacial distances showed greater abilities for acid anhydride formation. Some discussions were given for these results.

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Butenyl alkyl ethers (BE) were polymerized in toluene by BF₃·O (C₂H₅)₂ at-78°C. Although BE has a bulky ethyl group in β-position of its olefinic double bond, low molecular weight polymers were easily produced. In the polymerization of ethyl and isopropyl BE, a crystalline polymer was obtained from the trans-isomer.

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To study the effect of alkoxyl group on the polymerizability of vinyl ethers in the cationic polymerization, copolymerization of vinyl ethers was carried by BF₃·O (C₂H₅)₂in toluene or methylene chloride at -78°C. Relative reactivity of vinyl ethers was calculated from the rate of monomer consumption measured by the gas-chromatographic method. The reactivity of alkyl vinyl ethers (CH₂=CHOR) was found to be in the following order irrespectively of the kind of solvent,
R: t-butyl<i-propyl<ethyl<n-butyl≥i-butyl<methyl.
This order coincides with that of the reactivity for acidic hydrolysis. However, the order of reactivity of ethyl, n-butyl and i-butyl vinyl ethers had no correlation with the polar effect of alkoxyl group. These results suggest that the reactivity of vinyl ether is affected by the steric effect as well as the polar effect of alkoxyl groups.

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In an attempt to synthesizeα-polypeptide by the hydrogen migration polymerization of acrylamide derivatives which carry an electron-withdrawing substituent at a β-carbon, trans-ρ-nitrocinnamide and trans-β-chloracrylamide were prepared and polymerized with basic initiators. Trans-ρ-nitrocinnamide was polymerized to a polymer with an intrinsic viscosity of about 0.09. About one third of the structural units in the polymer were linked by peptide bonds. Existence of the α-peptide linkage was confirmed. Trans-cinnamide was found to give only a β-polypeptide. This indicates that a strongly electron withdrawingρ-nitro group is necessary to induce α-polypeptide formation. Trans-β-chloracrylamide was polymerized to a polymer with an intrinsic viscosity of about 0.1. About one fourth of the structural units in the polymer were linked by peptide bonds. It is not known, however, whether the peptide linkage isαorβ.

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D (+) Propylene oxide was polymerized by diethylzinc-water system at various Zn/H₂Oratios. Polymers obtained were fractionated with acetone at 0°C, and the specific rotation, [α] D of the fractionated polymers was measured. The optical activity of the crystalline part of the polymers remained unchanged at any Zn/H₂O ratios, whereas [α] D of the amorphous part decreased with decreasing the ratio of H₂O to ZnEt₂In copolymerizations of epichloropydrin with tetrahydrofuran by the ZnEt₂-H₂O system, it was found that epichlorohydrin content in the polymers formed at the later stage of the polymerization was significantly larger compared with polymers formed at the initial stage. From these facts, it was concluded that two types of active species, cationic and anionic, are operative in the polymerization system of epoxides initiated by ZnEt₂-H₂O catalyst (Zn/H₂O>1).

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