Radiation-induced polymerization of 1,2-cyclohexene oxide in the plastic crystalline state

Radiation-induced solid state polymerization of 1,2-cyclohexene oxide has been investigated. By the differential thermal analysis and x-ray diffraction analysis, it was found that this compound has a phase transition point at ?81°C and behaves as a plastic crystal in the temperature range from ?81°C to ?36°C (melting point). The in-source polymerization proceeded not only in the plastic crystalline state but also in the ordinary crystalline state at temperatures below the phase transition point. The overall rate of polymerization and the rate of chain transfer to monomer in the plastic crystalline state were larger than those in the ordinary crystalline state by a factor of about forty, but the kinetic mechanisms were identical, i.e., the termination mechanisms were unimolecular in both solid states. In contrast, the kinetic mechanisms in the plastic crystalline state and in the liquid state were different. From these observations, the effects of molecular motion and molecular arrangement on the polymerizations of 1,2-cyclohexene oxide in the three phases were discussed.     

Four-center type photopolymerization in the crystalline state. VI. Kinetic and structural study of the polymerization of p-phenylenediacrylic acid diethyl ester

The effect of temperature on the four-center type photopolymerization has been investigated for p-phenylenediacrylic acid diethyl ester over a wide temperature range including crystal transition point (56°C) and melting point (96°C) of monomer. With the elevation of temperature between ?50 and 15°C, the polymerization rate in the initial stage increased and the degree of polymerization decreased monotonously, while the rate in the later stage decreased above ?25°C. With irradiation at above 25°C, the monomer crystals became sticky, and the polymerization was suppressed at the stage of oligomerization with low conversion. This tendency was enhanced above the crystal transition point, giving mainly dimer in low yield. Above the melting point, only radical polymerization occurred with the aid of oxygen. The steric configuration of the products in the crystalline state was 1,3-trans with respect to the cyclobutane ring. Peaks in NMR spectra of all products were assigned to the protons involved in four compounds up to tetramer. Various results obtained have been interpreted in terms of the change, as a function of temperature, from a topochemical polymerization which proceeds under a control of the monomer lattice to a photoinitiated vinyl-type polymerization in the disordered state. It is concluded that a rigid crystal lattice is indispensable for the four-center type photopolymerization to proceed smoothly.     

Polymerization and viscoelastic behavior of networks from a dual‐curing,liquid crystalline monomer

The network formation and viscoelastic behavior of a liquid crystalline monomer, whose structure includes both acrylate and acetylene reactive groups, have been studied. By combining both photo and thermal polymerization, the networks can be formed in two separate steps, with the initial photopolymerization dominated by acrylate crosslinking and subsequent thermal polymerization dominated by acetylene crosslinking. In addition, the monomer exhibits a liquid crystalline phase. Photopolymerization while in the liquid crystal phase locks in the molecular ordering. Dynamic mechanical analysis shows that networks formed from the liquid crystalline phase have lower crosslink densities and narrower distributions of molecular weights between crosslinks when compared to networks formed from the isotropic phase (and at higher polymerization temperatures). After thermal postcure at 250°C, the networks formed from the isotropic monomer have a 23% higher dynamic mechanical storage modulus (in the glassy state) than the networks formed from the liquid crystalline monomer. The thermally postcured networks have unusually high glass‐transition temperatures, which exceed 300°C. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1183–1190, 1999     

Polymerization of Acrylonitrile-Metal Haiide Complexes in the Frozen State. III. Relationship between Rate of Radiation-Induced Polymerization and Complex Concentration

Radiation-induced polymerization of acrylonitrile (AN) in the ZnCl₂-AN-H₂O ternary system was carried out at temperatures ranging from 30 to ?78°C, and correlation between the polymerization rate and the concentration of complexed AN with zinc atom was clarified. The selected systems were in the supercooled liquid state at ?78^CC with the molar composition ratio of ZnC12:AN:H₂O of 1:1:3. The polymerization is free-radical in character. The 0.5-power dependence of the polymerization rate on the dose rate at 30°C indicates bimolecular termination, while the 0.9-power dependence at ?78°C shows predominant unimolecular termination because of the high viscosity of the systems at Just above the glass transition temperature. The negative temperature dependence of the polymerization rate is indicative of the tendency of the complex concentration to increase with lower temperatures. The polymerization rate, therefore, is proportional to the 2 and 1.5 powers of the complex concentration at ?78 and 30°C, respectively. These results indicate participation of the complexed monomer both in generation of the initiating radical species on irradiation and in the propagation step. A kinetic scheme has been proposed on the basis of the results.     

Photoinduced ionic polymerization. VII. Cationic polymerization of cyclohexene oxide in solid state

Photopolymerization of cyclohexene oxide in the presence of electron acceptors was studied in a bulk system (in liquid as well as in solid states). The polymerization was proved to proceed by a cationic mechanism in both states by the effect of inhibitors. In a liquid phase the light intensity dependence of the rate of polymerization and the molecular weight distribution showed a contribution of a free ionic polymerization. Any discontinuous phenomenon in the rate as well as in the molecular weight was not discerned between liquid(above ?36°C) and plastic crystal (between ?36 and ?81°C) phases. A quantum yield of monomer consumption as high as 8 × 10³ was observed in the plastic crystal phase. Below ?81°C in the normal crystal phase the rate as well as the molecular weight was remarkably suppressed.     

Thermal transition of a wholly aromatic thermotropic liquid crystalline copolyester

A copolyester was prepared from p-hydroxybenzoic acid (HBA), 2,6-naphthalene dicaboxylic acid (NDA), and hydroquinone (HQ). Thermal transition behavior and the crystal structure of this copolyester were investigated by using polarized light microscopy (PLM), differential scanning calorimetry (DSC), and wide-angle X-ray diffraction (WAXD) after annealing at solid-phase polymerization conditions. A glass transition or newly ordered structure in the 270–290°C range was observed on annealing at 260°C, which increased with annealing time, attributed to mobility and reactive rearrangement in amorphous regions. Broad and unclear WAXD profiles and multimelting behaviors were found on annealing at 280°C, and explained by hexagonal and orthorhombic lattice formation and transformation. A large increase in melting temperature was observed only on annealing at a temperature (320°C) near the crystal–nematic transition, suggesting annealing temperatures near the melting point are required for sufficient mobility to afford crystalline rearrangement via transesterification. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3763–3769, 1999     

Crystallization during polymerization of poly-p-xylylene. II. Polymerization at low temperature

The polymerization of p-xylylene was followed with a newly designed differential thermal analysis system at temperatures between ?196°C and ?20°C. It was found that at the lower temperatures the monomer condenses first to the crystalline monomer before simultaneous polymerization and crystallization. At the higher temperatures, polymerization and crystallization are successive. The data are in agreement with the morphology and crystal structure data derived in Part I of this series of papers on crystallization during polymerization of poly-p-xylylene.     

Dipolar motions and phase transitions in a side‐chain polysiloxane liquid crystal. A study by thermally stimulated depolarization currents

The relaxation mechanisms present in a side‐chain liquid crystalline polymer have been studied by Thermally Stimulated Depolarization Currents (t.s.d.c.), in a wide temperature range covering the glassy state, the glass transition region, and the liquid crystalline phase. The thermal sampling procedure was used to decompose the complex relaxations into its narrowly distributed components. Three relaxation mechanisms were observed in this polymer: a relaxation below the glass transition temperature that is broad and extends from −150°C up to −110°C, the glass transition relaxation whose maximum intensity appears at ∼20°C, and a relaxation above the glass transition temperature, in the liquid crystalline phase. The attribution of these relaxations at the molecular level is discussed. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 227–235, 1999     

The possible existence of the ferroelectric state of supercooled water

A second-order phase transition into the ferroelectric state was shown to occur in liquid water at −40°C. This finding was in agreement with several experiments with supercooled water, in which physical value singularities were observed at the specified temperature. The known maximum of water density at +4°C is a result of the joint action of thermal expansion and density fluctuations caused by closeness to the phase transition point.     

Cyclopolymerization. VI. Polymerization mechanism of N-methyl-N-allylmethacrylamide at lower temperature

Mechanistic investigations on the polymerization of N-methyl-N-allylmethacrylamide (MAMA) at lower temperature were carried out based upon the ESR studies of MAMA and its monofunctional counterparts irradiated with ⁶⁰Co γ rays. Cyclopolymerizability of MAMA was also studied in connection with the hindered rotation about its amide C? N bond. The propagating radical observed is only related to the methacryl group but not to the allyl group both in MAMA and its monofunctional counterparts. Polymerization at ?78°C yielded a polymer with a lower degree of cyclization(88.8%) as compared with that of polymers formed at higher temperatures (93.5% above 0°C). A structural study revealed that the increment of the unsaturation in the poly-MAMA obtained at ?78°C is due to the allyl group and the content of pendant methacryl group is almost unchanged over the temperature range from ?78 to 120°C. These results led to the conclusion that the polymerization of MAMA at ?78°C proceeds mainly through the methacryl group, the rate-determining step is the cyclization reaction, and, in addition, cyclization reaction scarcely occurs when it polymerizes through the allyl group. Since MAMA is frozen into a glassy state, the effect of glass transition temperature (T_g) has been studied and it was suggested that the polymerization of MAMA proceeds only above T_g.     

Molecular weight distributions in radiation-induced polymerization. VI. γ-ray-induced polymerization of “dry” styrene in the solid state

The γ-ray-initiated polymerization of styrene in the solid state has been studied over the temperature range ?35°C to ?55°C for samples exhaustively purified and dried to remove residual water (“dry” samples). Comparison with kinetic results previously reported for dry samples in the liquid state indicates a sharp decrease in the rate of polymerization resulting from the liquid to solid state transition. The molecular weight distributions for in-source polymerization at ?35°C and ?40°C are bimodal in nature, and the appearance of a third peak is noticeable at ?47°C and ?55°C. In the case of postpolymerization at ?35°C the molecular weight distribution is bimodal as in the case of in-source samples. In the former case, however, the high molecular weight peak is predominant whereas the low molecular weight peak predominates in the latter. These results have been tentatively attributed to the postulated coexistence of two distinct propagating species which are radical and cationic in nature.     

Polymerization in lyotropic liquid crystals. I. Change of structure during polymerization

Polymerization was made at 60°C in a lyotropic liquid crystal of sodium undecenoate and water. The liquid crystalline structure prior to polymerization was identified by optical microscopy and low-angle x-ray diffraction as an array of hexagonal closely packed cylinders with the hydrophobic part of the soap in the center of the cylinders. During polymerization the structure became isotropic at 60°C. Cooling to 20°C transformed the structure to a lamellar liquid crystal–a reversible transition. The structure of the lamellar phase was interpreted as a polyethylene backbone from which deformed decanoate chains reached toward the aqueous layer. Molecular models showed the model to accept head-tail, head-head, and tail-tail configurations in cis and trans conformations with the exception of the cis tail-tail configuration.     

The crystalline character of atactic poly(p-biphenyl acrylate) and poly(p-cyclohexylphenyl acrylate) in their dynamic mechanical response

Dynamic mechanical properties have been determined in atactic poly(p-biphenyl acrylate) (PPBA) and poly(p-cyclohexylphenyl acrylate) (PPCPA) in the temperature range from 80 to 540°K at frequencies in the range 10³–10⁴ Hz. The general behavior of the dynamic elastic modulus as a function of temperature shows a transition region from the glassy state at about 390°K for both polymers, a plastic region extending over a temperature interval of about 100°K, and another transition to the melt situated at 540 and 480°K for PPBA and PPCPA, respectively. The experimental data show that the mechanical behavior of both polymers strongly resembles that of crystalline polymers. The loss spectrum of PPBA shows the presence of several important maxima: one corresponding to the melting point, characterized by a very rapid increase of losses with increasing temperature (α′ relaxation), one in the glass-temperature range, characterized by a rather broad peak (α′ relaxation), and others below T_g, associated with secondary relaxation effects. The analysis of the different transitions and relaxations indicates that some of these processes can be ascribed to motions taking place in the ordered regions of the polymer. PPCPA shows a similar loss pattern; however, owing to the lower melting point the α maximum is partially submerged in the α′ relaxation associated with the melting process. Of particular interest is the γ process in the glassy state of this polymer, caused by the chair–chair transition of the cyclohexyl rings. The limited intensity of this relaxation as compared with that of most polymers containing cyclohexyl side groups, has been interpreted as due to the high ΔF associated with such a transition for cyclohexyl rings linked to phenylene groups. This leads to some interesting conclusions about the conformation of the side groups in PPCPA.     

Structural transformations of supercooled water in nanopores, studied by microwave radiation

It is shown that the state of supercooled water in nanoporous materials can be studied by measuring the attenuation of microwave radiation. By analyzing variations in the intensity of radiation transmitted through a moistened medium during the supercooling of water in the range of ?37 to ?190°C, the temperatures at which structural transformations take place can be determined. Using the example of KSKG silica gel with a mean pore size of 8 nm, it is shown that at a moisture of 3?C18%, water is found in the liquid state up to a temperature of ?130°C, at which the transition to glass occurs.     

Effects of temperature and water on the γ → α crystalline transition of nylon 6 caused by stretching in the chain direction

The effects of temperature and water on the crystal transition of nylon 6 from the γ phase to the α phase, which is caused by stretching along the chain direction, were investigated. The γ-phase fibers with high crystallite orientation were stretched at constant load under various conditions. An inversion of the effect of water on the transition occurs at about ?60°C. Stretching in the wet state is more effective for the transition at higher temperature. In contrast, at low temperatures water in the crystalline regions actsasa cohesive agent for the chains and increases the activation energy for the transition. Thus, dry stretching is more effective than wet stretching at very low temperature. The fraction of transformed α-phase crystallites increases abruptly over a narrow range of stress. Thus the critical stress can be determined for the transition. The critical stress changes appreciably with temperature; the higher the temperature, the lower the critical stress. The relation between stretching temperature and critical stress was analyzed by Flory's equation for the shift of transition temperature by stress. About 220°C. was estimated as the zero-stress transition temperature. The heat content of the γ-phase crystal was estimated to be smaller by 500 cal./mole than that of the α-phase crystal. This result suggests that the free energy of the γ-phase crystal is lower than that of the α-phase crystal at temperatures lower than the transition point. The irreversible strain of a sample in which the crystal transition has taken place is very small at low temperature. This small extension of the sample is evidence that the γ → α transition produced by stretching along the chain axis is a crystal-crystal transition.     

Polymerization of fluorinated diacetylenes

Perfluoroalkylene diacetylenes, HC?C? (CF₂)_n? C?CH, underwent thermal polymerization at 250–350°C to give glassy polymers stable to 450°C. Partial polymerization of the volatile monomers gave oligomers that are processable at atmospheric pressure. Polymers with similar thermal stability were obtained by transition-metal-catalyzed polymerization of the monomers at moderate temperatures.     

Solid-State Polymerization in Binary Component Systems at Low Temperature

Abstract

Radiation-induced polymerization in binary component systems of acrylonitrile-methacrylonitrile and acrylonitrile-vinyl acetate was studied at ?196°C. A mixture of two-component homopolymers was obtained from the acrylonitrile-methacrylonitrile system, which forms a eutectic mixture. When the mixture of acrylonitrile with vinyl acetate is cooled quickly from room temperature, a glassy state can be obtained. It was found that the copolymerization is possible in the glassy state at ?196°C, and the monomer reactivity ratios were determined as r ₁ = 6.0 and r ₂ = 0.2 (M ₁ = acrylonitrile), which coincides with the reported values on the radical copolymerization at room temperature.     

Higher aliphatic aldehyde polymers. VI. Poly(n-nonaldehyde)

Crystalline poly(n-nonaldehyde) (PNA) was prepared by anionic polymerization of n-nonaldehyde (NA) in methylcyclohexane (MCH) with lithium tertiary butoxide (LTB) as the initiator. Normal low-temperature conditions did not give polymer reprodusibly; however, when the polymerization was carried out with a gradual temperature decrease to ?60°C holding at this temperature followed by completion at ?78°C, a moderate yield of PNA was obtained. The polymer was acetate capped and characterized. Infrared and PMR spectroscopy, as well as degradation of the polymer in the presence of 2,4-dinitrophenylhydrazine to the hydrazone, conclusively proved the chemical structure of the polymer. VPO measurements and measurement of the inherent viscosity showed the polymer to be of moderate molecular weight. PNA is highly crystalline and shows two transition regions, one corresponding to the melting of the main chain at temperatures above 120°C and one region between 50 and 80°C, which is related to the crystallization of the aliphatic side chains. PNA, although inherently brittle, can be extruded through an orifice at a temperature near the side-chain melting temperature to give an extrudate whose x-ray patterns show the characteristics of a fiber diagram. It is suggested that the crystal structure of the PNA is similar to that of poly(n-heptaldehyde) but with a larger a spacing, which is expected from a longer aliphatic side chain.     

Relationship of deformation behavior to thermal transitions of ethylene/styrene and ethylene/octene copolymers

The stress‐strain response of low‐crystallinity ethylene‐octene (EO) and ethylene‐styrene (ES) copolymers with 7–20 mol % comonomer was compared over a temperature range that spanned the glass‐transition and crystal melting regions. Above the onset temperature of the glass transition, the copolymers exhibited elastomeric behavior with low initial modulus, uniform deformation to high strains, and high recovery after the stress was released. In the glass‐transition range, an initial low‐stress elastomeric response was followed by a distinct “bump” in the stress‐strain curve. On the basis of the temperature and rate dependence of the stress‐strain curve, local strain‐rate measurements, local temperature changes, and recovery characteristics, the “bump” was identified as high strain yielding. Hence, the stress‐strain curve sequentially exhibited the features of elastomeric and plastic deformation. Following high strain yielding, strain hardening dramatically increased the fracture strength. This behavior was defined as elastomeric‐plastic. Elastomeric‐plastic behavior in the broad glass‐transition range constituted a gradual transition from elastomeric behavior at higher temperatures to low‐temperature plastic behavior with high modulus and macroscopic necking. Because of the lower glass‐transition temperature of EO, ?40 °C as compared with ?10 °C for ES, the onset of elastomeric‐plastic behavior occurred at a significantly lower temperature. The concept of a network of flexible chains with fringed micellar crystals serving as the multifunctional junctions that provides the structural basis for elastomeric behavior of low‐crystallinity ethylene copolymers was extended to elastomeric‐plastic behavior by considering a network with a fraction of rigid, glassy chains. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 40: 142–152, 2002     

Polymerization of para-xylylene derivatives (parylene polymerization). II. Heat effects during deposition of parylene C at different temperatures

Thermal effects accompanying vacuum deposition of poly(chloro-para-xylylene) in the temperature range between ?196 and 0°C have been studied using two separate methods. One is based on the recording of the rate of evaporation of liquid nitrogen and it is used for the deposition at ?196°C, and the second involves the recording of changes in the substrate temperature and is used for the deposition in the range of ?162 to 0°C. These methods enable us to observe two distinct effects: fast (discrete), resulting in the appearance of sharp, exothermic spikes; and slow (continuous), resulting in the shift of the baseline. The shift of the baseline exhibits a well-defined maximum at about ?65°C and this temperature is attributed to the melting point of the monomer. The fast process always occurs below this temperature and is explained as a solid state, chain addition polymerization. The quantification of the heat effect at ?196°C strongly suggests that the quinonoid form of the monomer participates in the propagation step of this chain reaction. The fast (solid state) and the continuous modes of polymerization may occur simultaneously in the range of about ?140 and ?65°C. The frequency of the initiation which is the formation of dimer radical seems to control the occurrence of these two modes of polymerization.