Effect of acetylene on the γ-radiation-induced polymerization of ethylene

The effects of acetylene on the γ-radiation-induced polymerization of ethylene were studied from the viewpoint of the gaseous products and polymer structure. The experiments were carried out under a pressure of 400 kg/cm²; the temperature was 30°C; the does rate was 1.1 × 10⁵ rad/hr; and the acetylene content was 0–20%. The solid polymer was obtained in the polymerization of ethylene containing 2.2% acetylene, while the monomer containing 19.7% acetylene gave a yellowish viscous oil. The polymer yield and molecular weight decreased remarkably with acetylene content. The main gaseous product was hydrogen, and trace amounts of butane, butene-1, butadiene-1,3, and benzene and its derivatives were also observed. The rate of formation of hydrogen was almost independent of acetylene content and there was no difference in acetylene contents before and after the irradiation was found. The infrared spectra of the polymers showed the presence of vinylidene, trans-vinylene, and terminal vinyl unsaturations, 1,4-disubstituted benzene, and carbonyl groups. The contents of trans-vinylene, terminal vinyl, and methyl groups increased with acetylene content, and that of vinylidene was independent of acetylene content. The monomer reactivity ratios of ethylene and acetylene were evaluated as 45.5 and 66.0, respectively. On the basis of the results, the effects of acetylene on the γ-radiation-induced polymerization of ethylene were discussed.     

Kinetic study of γ-radiation-induced polymerization of ethylene in the presence of acetylene

The effects of acetylene on the γ-radiation-induced polymerization of ethylene were studied from the viewpoint of kinetics. The experiments were carried out under a pressure of 150–400 kg/cm²; the temperature was 30°C; the dose rates were 2.7 × 10⁴ and 1.1 × 10⁵ rad/hr; the acetylene content was 0–2.21%. Both the polymer yield and the molecular weight increased acceleratively with the reaction pressure in the polymerization containing 0.18% acetylene. The yield increased almost proportionally with the dose rate, and the molecular weight was found to be almost independent of the dose rate in the polymerization containing 2.21% acetylene. The polymerization rate and the molecular weight increased with reaction time, but the increment decreased with increasing acetylene content. The degree of increase in the molecular weight also decreased with increasing time. These results were analyzed by using a graphical evaluation method for kinetics, and the effects of acetylene on each elementary step in the polymerization discussed.     

Effect of hydrogen on the γ-radiation-induced polymerization of ethylene

The effects of hydrogen on the γ-radiation-induced polymerization of ethylene were studied from the viewpoint of polymer structure and kineties. All experiments were carried out at 30°C. In the polymerization of ethylene containing 21.6% hydrogen, the solid polymer was obtained as a main product, while no liquid product was found. There was no difference in hydrogen contents before and after the irradiation; and acetylene, ethane, butane, and butene-1 were found as gaseous products. The polymer yield increased almost proportionally with dose rate in the presence of 8.0% hydrogen; on the other hand the molecular weight was independent of dose rate. At hydrogen contents of 0–8%, the polymerization rate increased with reaction time and decreased with hydrogen content. The molecular weight also increased with the time, and the extent of the increment decreased with the time and hydrogen content. The number of moles of polymer chain increased proportionally with the reaction time and increased linearly with hydrgen concentration. These results were analyzed by using a graphical evaluation method for kinetics, and the effects of hydrogen on the each elementary step in the polymerization were discussed.     

Liquid carbon dioxide as a solvent for the radiation polymerization of ethylene

The usefulness of liquid carbon dioxide as a solvent for polymerization of ethylene was studied. The effect of liquid carbon dioxide on the polymerization was investigated under conditions of the pressure of 400 kg./cm.² over the temperature range 20–45°C. by using γ-radiation and AIBN as initiators. The infrared spectrum of the polymers showed that carbon dioxide had little effect on the polymer structure. The polymers contained no combined carbon dioxide and only small amounts of vinylidene unsaturation. The methyl content of the polymers was 0.5–4.0 CH₃/1000C. The polymer yield and molecular weight were found to be decreased by the addition of carbon dioxide in both polymerization by γ-radiation and AIBN. The number of polymer molecules formed per unit time increased with the content of carbon dioxide in the γ-ray polymerization, and was constant in the case of AIBN. The advantages of the use of liquid carbon dioxide as a solvent in this polymerization were also considered from the viewpoints of the continuous process, the separation of polymer, the stability of carbon dioxide to radiation, and commercial applications.     

Mechanism of initiation in the γ-radiation-induced polymerization of ethylene

The relation between the gaseous products and the reaction conditions such as pressure, temperature, and dose rate in the γ-radiation-induced polymerization of ethylene was studied. The main gaseous products were hydrogen and acetylene, and the amounts of these products increased linearly with reaction time, monomer density, and dose rate, while they were independent of reaction temperature. The ratio of rate of formation of hydrogen to acetylene was about one-half. Further, it was found that the number of moles of polymer chain formed was almost equal to that of acetylene at room temperature. An initiation mechanism in which both hydrogen and acetylene are formed is proposed. The equation which is derived on the basis of the initiation mechanism is shown to be in good accordance with the experimental results.     

Kinetics of the γ-radiation-induced polymerization of ethylene in liquid carbon dioxide

The γ-radiation-induced polymerization of ethylene with the use of liquid carbon dioxide as a solvent, was studied from the viewpoint of kinetics. The polymerization was carried out at conversions less than 10% under the pressure ranging from 100 to 400 kg./cm.², dose rates 1.3 × 10⁴?1.6 × 10⁵ rad/hr., and temperatures of 20–90°C. The concentration of carbon dioxide varied up to 84.1 mole-%. The polymerization rate and the polymer molecular weight were observed to increase with reaction time. This observation, however, becomes less pronounced with increasing concentration of carbon dioxide and with rising temperature. The exponents of the pressure and the dose rate were determined to be 2.3 and 0.85 for the rate, and 2.0 and ?0.20 for the molecular weight, respectively. From the kinetic considerations for these results, the effect of carbon dioxide on the initiation and termination reaction in the polymerization was evaluated.     

Two-stage irradiation study on propagation and termination in the γ-radiation-induced polymerization of ethylene in liquid carbon dioxide

The propagation and termination reaction in the γ-radiation-induced ethylene polymerization in liquid carbon dioxide were investigated by a two-stage irradiation. After irradiation at high dose rate, the polymerization occured at a considerable rate under the extremely low dose rate without initiation. The absolute propagation rate was determined in the second stage to be proportional to the square of ethylene fugacity and depended slightly on dose rate. The apparent activation energy for the propagation reaction is ?9 kcal./mole. From these observations which are the same as those in bulk polymerization, it is concluded that carbon dioxide acts as a diluent of ethylene monomer in the propagation reaction. Also, carbon dioxide was shown to be inactive to the growing radicals without irradiation, but oxygen which is produced by the radiolysis of carbon dioxide at high dose terminates the growing radicals with formation of carbonyl in the polymer.     

Initiation and propagation in γ-radiation-induced polymerization of ethylene

The initiation and propagation reaction in γ-ray-induced polymerization of ethylene was studied by the two-stage irradiation method, i.e., a first stage in which initiation and propagation occur at a high dose rate, and a second stage where only the growth of polymer radical occurs. The rate of initiation is calculated from the amount of polymerized monomer and the degree of polymerization as the rate of increase in the number of polymer chains. The initiation rate is shown to be proportional to the ethylene density in the reactor and dose rate. G_R of radical formation is found to be about 1.6 at 30°C. at a dose rate of 2.5 × 10⁴ rad/hr. and is almost independent of ethylene density but decreases slightly with increasing irradiation dose rate. The lifetime of the growing polymer chain radical is shown to be long at normal temperature. The absolute propagation rate is proportional to the square of ethylene fugacity and depends on dose rate to some extent. For chain growth, irradiation of low dose rate is necessary. The apparent activation energy for the propagation reaction is ?9 kcal./mole.     

Kinetics of γ-ray polymerization of formaldehyde in the presence of carbon dioxide

A kinetic study of the γ-ray polymerization of formaldehyde in toluene solution in the presence of carbon dioxide was carried out at temperatures of + 13 to ?17°C. Two modes of the polymerization, spontaneous and γ-ray polymerization, occur in this system. The γ-ray polymerization, experimentally separated from the spontaneous polymerization, was investigated. The rate of γ-ray polymerization increased slightly with the square root of carbon dioxide concentration. The rate of polymerization was also found to be proportional to the dose rate and the square of monomer concentration. The molecular weight of polymer formed was independent of the reaction condition. The apparent activation energy was estimated to be 10.3 kcal./mole. The kinetics of the γ-ray polymerization in the presence of carbon dioxide are explained quantitatively by a cationic mechanism, and the role of carbon dioxide is as an action of retardation for neutralization of the cationic initiating species, which was produced by γ-radiation, by means of a reverse reaction with an electron. Physical and mechanical properties of the polymer obtained by γ-ray polymerization were also investigated.     

γ-Ray-induced copolymerization of ethylene and vinyl chloride in liquid carbon dioxide

The γ-ray-induced copolymerization of ethylene and vinyl chloride with the use of liquid carbon dioxide as a solvent was studied under a total pressure of 400 kg/cm², with a dose rate of 2.5 × 10⁴ rad/hr at 30°C. A rubberlike, sticky polymer is obtained when the molar concentration of vinyl chloride is less than 30% in the monomer mixture, and the polymer is a white powder at higher concentrations of vinyl chloride. Infrared, x-ray, and differential thermal analyses confirm that the polymerization products are noncrystalline, true random copolymers. The rate of copolymerization decreases markedly when a small amount of vinyl chloride is added to ethylene monomer. In the range of vinyl chloride concentration higher than 5%, however, the rate and the molecular weight of copolymer increase with increasing concentration of vinyl chloride. It has been concluded from kinetic considerations based on these results that the rate of initiation increases proportionally with the concentration of vinyl chloride. Further, the growing chain radicals are shown to be deactivated by the cross-termination reaction between the radicals with terminal unit of ethylene and vinyl chloride, and no transfer reaction occurs.     

Short-chain branching in γ-radiation-induced polymerization of ethylene

In an attempt to elucidate the mechanism of chain-branch formation in the polymerization of ethylene, the effect of reaction conditions on short-chain branching in γ-radiationinduced polymerization of ethylene was investigated by using infrared spectroscopy. The concentration of methyl groups, i.e., the frequency of short-chain branching, increases with temperature and pressure and is independent of ethylene conversion to polymer and radiation intensity. The number of methyl groups per polymer molecule increases almost proportionally with the degree of polymerization. These facts indicate that short-chain branching occurs mainly by the mechanism of intramolecular hydrogen transfer. The effect of pressure on the rate of chain branching can be postulated by considering the transition state to be six-membered rings in hydrogen transfer reactions. The activation energy of chain branching is found to exceed that of propagation by 6 kcal./mole.     

Multichain copoly(α-amino acid). III. Multichain copoly(α-amino acid) prepared by the reaction of copoly(L-lysine γ-methyl-L-glutamate) with N-carboxy anhydride of β-benzyl L-aspartate

Graft copolymerization of N-carboxy anhydride of β-benzyl-L -aspartate onto copoly(L -lysine γ-methyl-L -glutamate) was carried out in N,N-dimethylformaide which contained 3 v/v% of dimethyl sulfoxide to obtain multi-N^ε-poly(β-benzyl-L -aspartyl)copoly(L -lysine γ-methyl-L gluta mate). The degree of polymerization of the branch chain attained was much influenced by the interval of the grafting sites of the copoly(L -lysine γ-methyl-L -glutamate). The solvent-induced two-step conformational transition of the multichain copoly(α-amino acid) was observed in the chloroform-dichloroacetic acid system at 25°C by the ORD technique. The stability of the α-helical conformation of the backbone polymer chain was decreased by the presence of poly(β-benzyl-L -aspartyl) branch chains that could form unstable α-helical conformations of opposite spirals.     

Diffusion and reaction in polyester melts

An understanding of the physical and chemical processes involved in the melt polymerization of polyesters in the higher inherent viscosity ranges is of fundamental importance in polyester preparation. For example, the volatile condensation product must diffuse to a polymer–vapor interface before polymerization can take place. Thus, the rate of polymerization of a polyester may be dependent not only upon the chemical kinetics of the polymerization reaction but also upon the diffusion of the condensation product through the polymer melt. The objective of the work presented in this paper was to determine to what degree diffusion or reaction kinetics, or both, limit the melt polycondensation of poly(ethylene terephthalate). Degrees of polymerization in melts between 0.0285 and 0.228 cm in depth at 270°C were measured for various reaction times and were compared with the predictions of mathematical models. The polycondensation rates under these conditions depend upon both the polycondensation rate constant k₁ and the diffusivity D of ethylene glycol through the melt. Estimates of the values to these parameters are: k₁ = 0.0500 (moles/mole of repeat unit)^?1 sec^?1; D = 1.66 × 10^?4 cm²/sec.     

Synthesis and characterization of poly(ethylene oxide‐co‐ethylene carbonate) macromonomers and their use in the preparation of crosslinked polymer electrolytes

Methacrylate‐functionalized poly(ethylene oxide‐co‐ethylene carbonate) macromonomers were prepared in two steps by the anionic ring‐opening polymerization of ethylene carbonate at 180 °C, with potassium methoxide as the initiator, followed by the reaction of the terminal hydroxyl groups of the polymers with methacryloyl chloride. The molecular weight of the polymer went through a maximum after approximately 45 min of polymerization, and the content of ethylene carbonate units in the polymer decreased with the reaction time. A polymer having a number‐average molecular weight of 2650 g mol^?1 and an ethylene carbonate content of 28 mol % was selected and used to prepare a macromonomer, which was subsequently polymerized by UV irradiation in the presence of different concentrations of lithium bis(trifluoromethanesulfonyl)imide salt. The resulting self‐supportive crosslinked polymer electrolyte membranes reached ionic conductivities of 6.3 × 10^?6 S cm^?1 at 20 °C. The coordination of the lithium ions by both the ether and carbonate oxygens in the polymer structure was indicated by Fourier transform infrared spectroscopy. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2195–2205, 2006     

Importance of the singlet–triplet transition of ethylene in its photopolymerization in the presence of oxygen

The rate of the photopolymerization of ethylene initiated by a mercury are lamp was investigated under a pressure of 400 kg/cm² at 30 ± 5°C by varying the wavelength of incident light. Ethylene was found to polymerize by ultraviolet light below about 3500 Å. The yield decreased gradually as the wavelength became longer, and no polymer was obtained at wavelength greater than 3900 Å. The addition of a small amounr (<100 ppm) of oxygen promoted the polymerization. Ultraviolet absorption spectat measured for the mixture of ethylene and a small amount of oxygen displayed several absorption peaks in the region 2700–3500 Å. The absorption began at about 3680 Å and became stronger with the concentration of oxygen. The average separation between the peaks was about 1000 cm^?1. The spectra were also measured for oxygen containing a small amount of ethylene. Similar absorption peaks with those described above were observed. On the basis of these results, it was pointed out that an excited triplet ethylene is formed under the irradiation of light due to a perturbing effect of oxygen contained in ethylene monomer and the reaction between the excited ethylene and oxygen is important in initiating the polymerization.     

Plasma polymerization of some organic compounds and properties of the polymers

Plasma polymerizations (under 13.5-MHz radiofrequency inductively coupled glow discharge) of some organic compounds are investigated by their properties (elemental analysis, surface energy, and infrared spectra) and their relations to the concentrations of free radicals in the polymers as detected by electron spin resonance (ESR) spectroscopy. Monomers that have been investigated are hexamethyldisiloxane, tetrafluoroethylene, acetylene, acetylene/N₂, acetylene/H₂O, acetylene/N₂/H₂O, allene, allene/N₂, allene/H₂O, allene/N₂/H₂O, ethylene, ethylene/N₂, ethylene oxide, propylamine, allylamine, propionitrile, and acrylonitrile. Plasma-polymerized polymers generally contain oxygen, even if the starting monomers do not contain oxygen. This oxygen incorporation is related to the free-radical concentration in the polymer. Molecular nitrogen copolymerizes with other organic monomers such as acetylene, allene, and ethylene, and their properties are very similar to those of plasma-polymerized polymers from nitrogen-containing compounds such as amines and nitriles. The addition of water to the monomer mixture reduces in a dramatic manner the concentration of free radicals in the polymer and consequently the oxygen-incorporation after the polymer is exposed to air. The concentrations of free radicals (by ESR) are directly correlated to the change of the properties of plasma-polymerized polymers with time of exposure to the atmosphere. These changes are primarily the introduction of carbonyl (and possibly hydroxyl) groups. The addition of water to the plasma introduces these groups during the polymerization.     

Cationic polymerization of formaldehyde in liquid carbon dioxide. Part I

A cationic polymerization of formaldehyde which gave a high molecular weight polymer was studied in liquid carbon dioxide at 20–50°C. In the polymerization without any catalyst both the rate of polymerization and the molecular weight of the resulting polymer increased rapidly with a decrease in the loading density of the monomer solution to the reaction vessel, and also increased with an increase in the initial monomer concentration. From these results it was concluded that the initiating species could be ascribed to an impurity contained in the monomer solution. Both the rate of polymerization and the degree of polymerization of the polymer also increased with rising temperature. The carboxylic acid added acted as a catalyst in the polymerization because of increase in the polymer yield, the molecular weight of polymer formed, and the number of moles of polymer chain with increasing dissociation constant of acid used. It was concluded that the polymerization in liquid carbon dioxide proceeded by a cationic mechanism. Methyl formate had no influence on the polymerization, but methanol and water acted as a chain-transfer agent.     

Copolymerization of carbon dioxide with propyleneimine

Carbon dioxide and propyleneimine were allowed to copolymerize without using any catalyst to give a polyurethane with a carbon dioxide content of 10–35 mole-%. The polymer yield, the specific viscosity, and the content of carbon dioxide in the copolymer increased with increasing polymerization temperature. The infrared spectrum of the copolymer showed the characteristic peak assignable to a cyclic urethane(4-methyl-oxazolidone-2) at 1750 cm^?1 as well as the peak characteristic of the urethane linkage at 1700 cm^?1. The relative intensity ratio of the former absorption to the latter decreased markedly with increasing polymerization temperature. Propyleneimine did not polymerize at all in the absence of carbon dioxide. Polymerizations were also carried out with the use of various solvents. On the basis of these results, a probable reaction scheme of the copolymerization was proposed.     

γ-Radiation-initiated post-polymerization of methacrylic acid in the solid state

The solid-state postpolymerization of slowly crystallized methacrylic acid was studied at 0°C with ⁶⁰Co γ-radiation as the initiator. The yield, molecular weight, molecular weight distribution, and stereosequencing of the polymer product were determined as a function of polymerization time. The narrow molecular weight distribution and the linear dependence of molecular weight on polymer yield were attributed to a polymerization mechanism characterized by both independent chain propagation and essentially no termination step. The overall polymerization rate was substantially faster than that reported previously for shock-crystallized monomer, a result which was attributed to termination by the occlusion of propagating radicals at defects in the shock-crystallized monomer. Although largely atactic, the polymer synthesized in the solid state contained a secondary kind of stereosequencing; the meso triad probability was highest at the end of the chain, where propagation had initiated and decreased continuously with chain growth. The gradient in stereosequencing along the chains was attributed to defects that were introduced into the monomer crystals by the growing polymer chains.     

γ-Ray-induced copolymerization of carbon monoxide with cyclic ethers

The γ-ray copolymerization of carbon monoxide with cyclic ethers, such as ethylene oxide, phenyl glycidyl ether, 1,3-dioxolane, 2-vinyl-1,3-dioxolane, terahydrofuran, 1,4-dioxane, and acetaldehyde was studied. A yellowish or brownish powdery copolymer was obtained in most of the cases examined. The infrared spectra showed that copolymers containing the ester structural unit were produced in the copolymerization with cyclic ethers which have no vinyl groups, and that a copolymer containing a ketone structure was produced from cyclic ether having vinyl group. It was found that the copolymer with ethylene oxide also had a β-propiolactone ring structure at the chain end or the side chain. The copolymers were confirmed to be partially crystalline from the x-ray diffraction diagrams. Further, a ring-opening polymerizability of the cyclic ether by γ-radiation was discussed. And it was found that as the bond dissociation energy between the carbon–oxygen linkage of the cyclic ether is small, the polymer yield both in the homopolymerization and copolymerization with carbon monoxide is high. A mechanism for the copolymerization is proposed on the basis of the results.