Solid-state polymerization of long-chain vinyl compounds. I. Effect of molecular arrangement on polymerizability of octadecyl methacrylate

γ-Ray-initiated postpolymerization of octadecyl methacrylate in polymorphic crystals and melt has been investigated to clarify the effect of molecular arrangement of the monomer on polymerizability. From thermal, x-ray, and infrared (IR) analyses this long-chain monomer exhibited three crystalline modifications that we refer to as α-, sub-α, and β-forms. The β-form (mp 28.7–29.7°C), which is obtainable from solution, is a stable state with triclinic chain packing. The α-form (mp 19.5–20.0°C), which is obtained first from the melt but transforms into β-form on storing, is a metastable state with hexagonal chain packing. The sub-α-form appears transiently in α→β transition. The polymerizability of octadecyl methacrylate in the β-form is extremely low, whereas the α-form can polymerize easily and the initial polymerization rate, saturated conversion, and polymer molecular weights increase with temperature. Polymerizability in the molten state at fairly high temperature is rather low, however. Thus maximum polymerizability is obtained just above the melting point of α-form. It has been found that particular orientation and suitable packing mode with some freedom of rotational motion of the monomer molecules in layered structure accelerate the polymerization reaction.     

Solid-state polymerization of long-chain vinyl compounds. IV. Effects of chain length on the polymorphic behavior and postpolymerization of n-alkyl methacrylates

Polymorphic behavior and γ-ray-initiated postpolymerization of the even-numbered long-chain Methacrylates (C₁₈-C₁₂) have been investigated. Phase transition behaviors of octadecyl, hexadecyl, tetradecyl, and dodecyl methacrylates are respectively, which become simpler with shortening of the chain length. The methacrylate monomers with sufficiently long hydrocarbon chains, such as octadecyl and hexadecyl, can be polymerized rapidly in the α-form crystal (hexagonal packing) by a fully two-dimensional mechanism, whereas in the β-form crystal (triclinic packing), polymerization can hardly occur. In the case of dodecyl methacrylate, however, an accelerated polymerization in the β form occurs after an induction period of several hours and the resultant polymer is gel-like. This can be interpreted by the propagation reaction across the polymer chain already formed. It has been found that the solid-state post-polymerization of n-alkyl methacrylates is affected by the chain length through the packing mode of the monomer molecules and also by the aggregation state of side chains in the resultant comblike polymer.     

Solid-state polymerization of long-chain vinyl compounds. III. Mechanism of γ-ray-initiated postpolymerization in layered structures of octadecyl methacrylate and acrylate

The mechanism and kinetics of the γ-ray-initiated postpolymerization of octadecyl methacrylate and acrylate in lamellar crystals were investigated by a simple model. This model assumes that the initiation points are distributed as in a checkerboard and that polymerization probability of the monomer molecules decreases conically around each initiation point. The two-dimensional polymerization can be characterized in this cone model by two parameters, a and r; a represents the polymerizability of the monomer for a given condition, and r depends on the number of initiation points per unit area. G values for the initiation reaction of octadecyl methacrylate and acrylate were estimated as 0.8 and 1.6, respectively. The two-dimensional postpolymerization of long-chain compounds proceeds in two stages. The rate of polymerization is very high and zero order with respect to monomer concentration in the first stage. It is lower and obeys first-order kinetics in the second stage. The rate constants of the zero-and first-order polymerizations were k_p0 = 1.73 molecule sec^-1 and k_p1 = 0.93 sec^?1, respectively, for octadecyl acrylate at 20°C.     

Solid-state polymerization of long-chain vinyl compounds. VI. In-source polymerization of octadecyl acrylate by γ-ray irradiation

The in-source polymerization of octadecyl acrylate in the lamellar crystal (hexagonal packing) by γ-ray irradiation has been investigated, as compared with the two-step and one-step postpolymerizations. The viscosity-average molecular weight is very high even in the initial stage and is practically saturated after 3–5 hr, although the conversion increases successively with time. The molecular weight distribution of poly(octadecyl acrylate) obtained by in-source polymerization is very wide (M _w/M _n = 13.1, at 20°C). The results of in-source polymerization of the long-chain vinyl compounds can be interpreted using the cone model for polymerization probability, similar to those of one-step and two-step postpolymerizations.     

Influence of molecular arrangement on the γ-ray-irradiation solid-state polymerization of 1-octadecyl vinyl ether with a characteristic polymorphism

The polymorphic behavior of 1-octadecyl vinyl ether was investigated by DSC and X-ray diffraction measurements under various temperatures. In DSC measurement of 1-octadecyl vinyl ether in the temperature range of −30 to approximately 50°C, four transition peaks were observed on heating, whereas three transition peaks appeared on cooling. The phase-transition behavior was investigated by the repeating scanning DSC measurements. It was concluded that this compound exhibited four crystalline modifications: α, sub α, β₀, and β₁. It was confirmed by the temperature-controlled X-ray diffraction measurement that these phase transitions are attributed to the change of crystal systems from hexagonal packing (α form) to a distorted orthorhombic (O⟂′) system (β₁ form) via orthorhombic (O⟂) (sub α form) and intermediate β₀ form, although the β₀ form has not yet been clarified. In the γ-ray-irradiation solid-state polymerization for these crystal forms of this compound, the polymerizability of the sub α form is higher than that of other forms, and that of the α form is lowest. The polymerizability demonstrated an unusual increase at a temperature of −83.6°C, probably because the cationic polymerization mechanism is dominant over that of the free radical. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3845–3853, 1999     

Solid-state polymerization of long-chain vinyl compounds. V. Two-step postpolymerization of octadecyl acrylate by temperature increase and by stepwise γ-ray irradiation

The mechanism of two-dimensional polymerization of octadecyl acrylate in lamellar crystal was investigated in two-step postpolymerizations by temperature increase and stepwiseγ-ray irradiation in lieu of the usual one-step reaction. Two-step postpolymerizations by these procedures are interpreted satisfactorily by the cone model, which assumes that the polymerization probability of the monomer molecules in a single layer is distributed conically around the initiation point. It was found that the propagating radicals were living, even in the saturated stage, and the effect of the polymer chains already formed on the propagating and terminating reactions was evident. Furthermore, molecular weight distributions of the resultant poly(octadecyl acrylate) measured by gel permeation chromatography (GPC) were broad. The values of M_w /M _n for the two-step post polymerizations were 4.71–7.03, whereas those for one-step reactions were 3.26–5.54.     

Spontaneous formation of polypeptides in the interfacial thin films of amphiphilic amino acid esters: acceleration of the polycondensation and control of the structure of resultant polymers

For the purpose of elucidating the effects of molecular arrangements on the reaction rates and the structure of products, polycondensation of long-chain esters of alpha-amino acids in the monolayer on the water surface and the LB multilayers deposited on CaF2 plates were investigated by monitoring changes of the IR spectra. Spontaneous formation of the polypeptides occurs in the mono- and multilayers at room temperature without any catalyst. The rates of polycondensation in the monolayers are markedly influenced by the degree of molecular packing. Maximum polymerizability is obtained in the vicinity of the transition region from expanded to condensed films. The rates of polycondensation in the LB films are much higher than those in the bulk solids and the molten states. The polycondensation seems to be accelerated by regular arrangements of the monomer molecules in the LB films, where the functional groups are concentrated and situated more effectively for the reaction than in the bulk states. However, the polycondensation rates in the LB films are considerably slower when compared with those in the monolayers on the water surface kept at the optimum area or surface pressure, because the molecules in the LB films deposited under high compression are packed more closely than the optimum condition. Thus, suitably close packing of the monomer molecules, retaining a particular orientation together with some conformational freedom in the monolayer, is most favorable for the polycondensation. Two probable mechanisms for the polycondensation in the Y-type multilayers have been proposed. In the assembly of head-to-head double layers of the monomer molecules, the interlayer reaction propagates by sewing up the functional groups facing each other in the adjacent layers, and the polypeptide of a helical structure or random coil can be obtained. In contrast, for the alternating assembly of the amino acid ester and non-polymerizable octadecyl acetate, the polycondensation should proceed only in each single layer (intralayer reaction) and the polypeptide of the extended beta-form can be formed. In the case of dioctadecyl glutamate LB films, as well as the monolayer on water, the resultant polypeptide is the comb-like polymer with unreacted long-alkyl ester groups as side chains and abundant in the beta-form, indicating the dominant intralayer reaction. On the other hand, in the Y-type multilayer of the equimolar mixture of dioctadecyl glutamate (with two ester groups) and octadecyl ester of lysine (with two amino groups), both of the intra- and interlayer reactions occur effectively, resulting in a two-dimensional network structure of the polypeptide. In conclusion, not only the rate of polycondensation but also the higher-order structure of the resultant polypeptides can be controlled by organized arrangements of the monomer molecules in the interfacial thin films.     

Stereospecific polymerization of benzyl α-(alkoxymethyl) acrylates

α-(Alkoxymethyl) acrylates, such as methyl α-(phenoxymethyl) acrylate, benzyl α-(methoxymethyl)acrylate (BMMA), benzyl α-(benzyloxymethyl)acrylate, and benzyl α-(tert-butoxymethyl)acrylate, were synthesized, and their polymerizability and the stereoregularity of the polymers obtained by radical and anionic methods were investigated. The radically obtained polymers were found to be atactic by ¹³C- and ¹H-NMR analyses, but the polymers obtained with lithium reagents in toluene at −78°C were highly isotactic. Further, it is noteworthy that isotactic polymers were also produced with lithium reagents even in tetrahydrofuran. Effects of polymerization temperature and counter cation on stereoregularity were clearly observed in the polymerization of BMMA, and a potassium reagent afforded an almost atactic polymer. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 721–726, 1997     

Probing structural transition and guest dynamics of hydroquinone clathrates by temperature-dependent terahertz time-domain spectroscopy

The structural transition from hydroquinone clathrates to crystalline α-form hydroquinone was observed up to the range of 3 THz frequency as a function of temperatures. We found that all three hydroquinone clathrates, CO(2)-, CH(4)-, and CO(2)/CH(4)-loaded hydroquinone clathrates, transform into the α-form hydroquinone at around 102 ± 7 °C. The resonance peak of the CO(2)-loaded hydroquinone clathrate at 2.15 THz decreases with increasing temperature, indicating that CO(2) guest molecules are readily released from the host framework prior to the structural transformation. This reveals that the hydroquinone clathrates may transform into the stable α-form hydroquinone via the metastable form of guest-free clathrate, which depends on guest molecules enclathrated in the cages of the host frameworks. A strong resonance of the α-form hydroquinone at 1.18 THz gradually shifts to the low frequency with increasing temperature and shifts back to the high frequency with decreasing temperature.     

Polymerization of amphiphilic quaternary ammonium salts of acrylic,methacrylic, and ethacrylic acids

The polymerization behavior of dodecyltri-methylammonium methacrylate, and hexadecyltrimethylammonium acrylate, methacrylate and ethacrylate as amphiphilic monomers bearing a polymerizable double bond outside the micelle shell was investigated in micellar solution. Although the monomers did not have spontaneous polymerizability, they polymerized in the presence of both oil-soluble and water-soluble radical initiators, in spite of the difference of the expected location solubilizing initiator molecules. The profit based on micelle-forming of the monomer on the polymerization in water disappeared by the addition of sodium chloride into the polymerizing system due to the increased dissociation between cationic micelles and the polymerizable counter ions.     

Polymerizability and related problems in the anionic polymerization of lactams

The anionic polymerization of lactams at low temperatures is not governed by thermodynamic equilibrium between the cyclic monomer and the linear polymer. On the basis of our reaction mechanism we propose therefore a new criterion (in contrast to the thermodynamic one) for estimating the chemical polymerizability of lactam: k_endo/k_lactam, where k_lactam is the rate constant of alkaline hydrolysis of the lactam and k_endo that of the endocyclic imide bond in the corresponding N-acyl lactam. The value thus found for α-piperidone and giving the theoretical polymerizability of this lactam accounts, however, only partially for its low polymerizability. Finally, the behavior of α-piperidone derivatives in α-pyrrolidone polymerization, as well as that of α-pyrrolidone and α-piperidone in polymerization in the presence of inorganic salts such as LiCl and LiSCN, shows that the unusually low ability of this lactam to polymerize could be explained in terms of the hydrogen-bond-rich structure of the resulting polymer appearing at a lower stage of conversion than that of other lactams and which might encage the active site situated at the end of the growing chain and thus hinder the access of lactam anion.     

Thermodynamics of Addition Polymerization Processes

The polymerizability of compounds such as 1,l-disubstituted ethylenes, aldehydes, ketones, isocyanates, and five- and six-membered ring compounds is determined largely by thermodynamic considerations. The transition from non-polymerizability to polymerizability, correspondlng to a change in the sign of ΔG, is often quite sharp. Factors which generally make the free energy of polymerization more negative, and which therefore favor polymerization, are low temperature, high pressure, and high monomer concentration. Additional driving force is sometimes available if the monomer is in the supercooled (glassy) state rather than the crystalline state, or if the polymer crystallizes on formation. Alkyl substituents have an unfavorable effect on polymerizability; halogen substituents have a favorable effect. Many monomers which do not homopolymerize for thermodynamic reasons will copolymerize with a second monomer to the extent of forming copolymers containing 50 or even 66 mol per cent of the first monomer.     

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 monolayers of vinyl and divinyl monomers

Monolayer balance techniques have been used to study “two-dimensional” polymerization of monomolecular films of octadecyl methacrylate and a divinyl ester. Polymerizations were initiated with ultraviolet radiation, and reaction rates and properties of the product evaluated from surface pressure–area isotherms. The polymerization rate of the acrylate in argon is linear up to 70% conversion; the product obtained in this way exhibits an isotherm which may reflect the packing and orientation of the starting monolayer. Rate data for the divinyl system—the product of which should be a sheet-like, two-dimensional analog of a network system—exhibit no unusual features.     

Structural transformation and guest dynamics of methanol-loaded hydroquinone clathrate observed by temperature-dependent Raman spectroscopy

The structural transformations and guest dynamics of methanol-loaded β-form hydroquinone (HQ) clathrate were investigated using temperature-dependent Raman spectroscopy. Methanol-loaded β-form HQ clathrate was obtained by recrystallization and characterized by elemental analysis, synchrotron X-ray diffraction, solid-state (13)C NMR spectroscopy, and Raman spectroscopy. Temperature-dependent Raman spectra of methanol-loaded β-form HQ clathrate were measured in the temperature range 300-412 K at increments of 4 K. Although no significant changes were evident in the temperature range 300-376 K, abrupt changes in the relative intensity and shape of the Raman bands were observed between 380 and 412 K indicating the structural transition from methanol-loaded β-form HQ clathrate to pure α-form HQ. Methanol molecules were gradually released from the β-form HQ clathrate in the range 364-380 K. Upon returning to ambient conditions, the crystal structure of the HQ sample remained identical to that of pure α-form HQ. Therefore, the temperature-induced structural transition of methanol-loaded HQ clathrate is completely irreversible and α-form HQ is more stable at ambient conditions.     

The role of intermolecular interactions in determining the mode of packing of crystalline polymers. Energy calculations on isotactic polypropylene

Packing energy calculations for isotactic polypropylene chains have been performed with the purpose: (a) to predict the most stable kind of monoclinic lattice for the α-modification; (b) to contribute to the understanding of the structural disorder which is commonly found in the α-modification; (c) to evaluate the order of magnitude of the differences in energies among the three modifications (α, β, γ) experimentally observed. The results for the α-form show that the best packing of the chains is achievable for the ordered P2₁/c space group, while more or less disordered structures may exist, which only slightly differ in energy from the most stable structure. In connection with point (c), our results are in agreement with the possibility of polymorphism in isotactic polypropylene.     

Polymerization of 1,3,5-trithiane in the solid state initiated by UV-irradiation. I. Polymerization conditions and polymer characterization

The solid-state 1,3,5-trithiane polymerization initiated by UV-irradiation was studied at various irradiation times and various polymerization temperatures. The conversion of monomer to polymer reaches limiting values (at longest) in about 30 min of reaction. The apparent activation energy of this process is somewhat higher than in the chemically initiated polymerization. Generated by UV, active centers, which initiate the polymerization, are stable. On the basis of X-ray diffraction studies it was found that the prepared polythiomethylene has a hexagonal structure and high degree of crystallinity. In the polymer investigated, a new additional crystal phase is formed, which is not stable.     

Ordered structures of poly(1H,1H,2H,2H-perfluorodecyl α-substituted acrylate)S

Ordered structures of poly(1H,1H,2H,2H-perfluorodecyl α-fluoroacrylate) (P17FF), poly(α-chloroacrylate) (P17FC), poly(methacrylate) (P17FM) and poly(acrylate) (P17FA) were investigated by X-ray diffraction, DSC and polarizing microscopic observations. At room temperature, both P17FF and P17FC prefer the layered structure of single-layer packing of the fluoroalkyl side chains, while P17FM contains both single-layer and double-layer packing, and P17FA forms double-layer packing. As temperature increases, particularly in P17FF and P17FC, there was observed a structural rearrangement of the single-layer packing to double-layer one accompanied by melting of the side chain crystallites, which may come from an intermolecular interaction between the main chains caused by polar effect of the α-substituents.     

Kinetic studies on the n-alkyl acrylate polymerization

Kinetic studies on the polymerization of n-butyl acrylate and n-octadecyl acrylate in toluene at 70°C with benzoyl peroxide as initiator are reported. High monomer orders of 1.55 and 1.75 were obtained for n-butyl and n-octadecyl acrylates, respectively. Though the initiator order in butyl acrylate polymerization was 0.5, the octadecyl acrylate polymerization showed less than square root initiator order. The activation energy for the polymerization of both the acrylates was determined. Autoacceleration was found even at low conversions. The autoacceleration was influenced by both monomer and initiator concentration. Molecular weight data was presented in support of the gel effect. © 1992 John Wiley & Sons, Inc.     

Hexagonal → cholesteric phase transition of DNA molecules in liquid-crystalline dispersion particles

To assess the character of packing of double-stranded (ds) DNA molecules in liquid-crystalline dispersion particles formed by phase exclusion of DNA molecules from aqueous salt solutions of poly(ethylene glycol), the circular dichroism spectra of these dispersions at different temperatures have been compared. It has been shown for the first time that heating dispersion particles with the hexagonal packing of ds-DNA molecules is accompanied by the hexagonal → cholesteric phase transition. This result can be described using the notion of quasi-nematic layers composed of orientationally ordered adjacent ds-DNA molecules in the structure of dispersion particles; these layers can be packed in two ways dictating their hexagonal or cholesteric spatial structure.