1994 рік

Previously described dendritic and hyperbranched polyesters and a new linear polyester obtained by polymerization of 3-hydroxy-5-(t-butyldimethylsilyloxy)benzoic acid, each based on the 3,5-dihydroxybenzoic acid building block, were used in the study of differences in chemical and physical properties between the three different polymer architectures. Comparison of the physical properties between the dendritic, hyperbranched and linear structures showed that thermal properties, such as glass transition temperature and thermogravimetric analysis, were independent of macromolecular architecture. However, the dendritic and hyperbranched materials demonstrated comparative solubilities which were much greater than that found for the linear polymer. Other differences were observed in chemical reactivities.

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The chemical modification of polyolefins in the melt, using free radical mechanisms suitable for reactive extrusion, was studied. An algorithm to approximate the solution to an equation for simultaneous random scission and crosslinking 1 is presented. This solution is compared to the classical two-step solutions of Saito 2-5, Flory 6 and Charlesby-Pinner 7, showing significant deviations for the simultaneous random scission and crosslinking case. Suggestions to improve further the scission term of this equation are presented. Experiments were performed using high density polyethylene and peroxides in a minitruder and in small ampoule reactors. Gel fractions, thermal properties and molecular weights were measured. The heats of transition and melting temperatures as measured by differential scanning calorimetry were found to decrease with increasing peroxide level but were independent of reaction temperature. A pure random crosslinking model was found to fit adequately the gel fraction data

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The main features of the critical line in presure-temperature-composition space for mixtures containing either a linear or a cyclic poly(dimethylsiloxane) (PDMS) in tetramethylsilane (TMS) are predicted through the use of the Patterson modification of Prigogine's corresponding-states theory, which incorporates the cell model of a liquid together with a simple van der Waals dependence of the configurational energy on volume. Two main kinds of critical lines are obtained: one is a continuous line for those mixtures with a small chain-length difference between the components, leading to a fairly good prediction of the liquid-vapour critical temperatures of the pure substances; and the other is a broken line for mixtures with a large chain-length difference between the polymer and solvent, indicating the occurrence of a lower critical threshold temperature (LCTT) at low polymer concentrations. A full set of temperature and pressure reduction parameters for both linear and cyclic oligomers and PDMS are reported, and are used as the basis for all the calculations with no adjustment whatsoever. It is predicted that the system of minimum chain length to show an LCTT is that containing a PDMS of 24 skeletal bonds, compared to the methane-hexane system in the n-alkanes, thus giving an insight into the more flexible and more expanded nature of the PDMS series. Results for the interaction parametert Zl confirm that any difference in chemical nature between TMS and the PDMS series may be largely ignored since the structural term ctz alone can account for the LCTT behaviour.

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The synthesis of rigid-rod poly([1.1.1]propellane)s and poly(p-phenylene)s with hydroxy functionalities in the side chains is described. The suitability of these hydroxy functions as anchor groups for dendritic fragments is investigated. Initial experiments show that not only oligophenylenes as model compounds but also the polypropellane can be dendrimerized to a high degree of conversion. The rigidity of the backbones is considered important in regard to this matter and is therefore addressed theoretically. Molecular modelling calculations based on the AMBER 3.0 force field show that, in fact, the polypropellane backbone is considerably rigid.

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The simple formula for the size distribution of additive sorption centres in polymers previously found experimentally is derived theoretically based on a two-component model of polymer structure

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The transesterification of three ethylene and alkyl acrylate random copolymers (alkyl=methyl, ethyl and n-butyl) with 3-phenyl 1-propanol (PPOH) was studied in 1,2,4-trichlorobenzene solution and in the melt. Various catalysts were used, with dibutyltin dilaurate (DBTDL) and dibutyltin oxide (DBTO) showing the highest activities. The reaction between the poly(ethylene-co-methyl acrylate) and PPOH in solution in a closed reactor confirmed that this reaction is reversible. When operated in the melt in a semi-open batch mixer at temperatures between 170 and 190°C the equilibrium was totally shifted to the product side due to effective removal of the lighter alcohols generated from the reaction. The mechanism and rate constants of reaction are identical, regardless of the reaction medium chosen. The reactivity of an alkyl acrylate group towards PPOH depends, to a large extent, on the chemical structure of the alkyl group, and it follows the order: methyl > ethyl > n-butyl. This is primarily attributed to the fact that the longer the alkyl group, the lower the electrophilicity of the carbonyl carbon of the acrylate, and the higher the steric hindrance, both being detrimental to the reactivity. The steric hindrance argument is supported by the activation energies observed in the presence of DBTO as the catalyst: 69.0, 81.6 and 96.6kJmot-1 for the methyl, ethyl and n-butyl, respectively. Mechanical mixing favoured the reaction rate.

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A number of poly(~-n-alkyl-L-aspartate)s, which are nylon-3 derivatives with an alkoxycarbonyl side group attached to every repeat unit, have been prepared by non-assisted anionic polymerization of the corresponding (S)-4-alkoxycarbonyl-2-azetidinones. Side reactions leading to imidation were found to take place to an extent which is highly dependent on both the polarity of the polymerization solvent and the nature of the alkyl side chain. Highly stereoregular polymers without detectable imidation and molecular weights in the range 105 to 5 ? 105 were obtained in dimethyl sulfoxide for n=4, 6, 8 and 12 and in CH2C12 for n= 1, 2 and 18 (n=number of carbon atoms in the alkyl side group). A study of the thermal stability of these new polyamides showed that they melt with decomposition to largely imidated polymers when heated at temperatures above 250°C. X-Ray analysis of oriented samples revealed that members with n = I, 2, 4 and 8 are able to form crystal structures with chains arranged in a helical conformation similar to the ~-belix typical of polypeptides. This type of conformation seems also to be adopted by all other members of the series. For n--6 and 12, however, the polymer chains did not crystallize but they became aligned side by side with alkyl side groups remaining in a disordered state.

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Light scattering and calorimetric techniques were used to investigate the isothermal phase behaviour of a ternary polymer blend consisting of three pairwise miscible homopolymers. These homopolymers, polystyrene (PS), poly(2-chlorostyrene) (P2C1S) and polycyclohexylacrylate (PCHA), are apparently the first known examples of homopolymers that form a closed loop in the ternary isothermal phase diagram. The phase diagram of the ternary blend was determined by light scattering at 433 K, where all three pairs are below their respective lower critical solution temperature (LCST). The miscible compositions exhibit a single glass transition temperature (Tg) which follow a simple volume additivity relationship. Inside the immiscible closed-loop region, single Tgs are also observed, but these are shown to be consistent with the presence of two phases. Two binary interaction parameters (for the pairs PS-P2C1S and PS-PCHA) were determined from the locations of LCSTs. The interaction parameter between P2C1S-PCHA was determined by approximating the observed closed-loop region of immiscibility by the Flory-Huggins lattice model. In analogy with systems comprised of a mixture of two polymers and a solvent, the closed-loop immiscibility gap results from an asymmetry in the interaction parameters between the three pairs (a 'Az' effect). The following ordering was observed: ZPCHA~2C1S

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Anisotropic homopolymerization of 2,5-dihydroxyterephthalic acid (DHTA) and 2,5-diamino-l,4-benzenedithiol dihydrochloride (DABDT.2HC1), and copolymerization of DHTA, terephthalic acid and DABDT.2HC1 in polyphosphoric acid (PPA), afforded high molecular weight rigid-rod polymer and copolymers, with two hydroxyl groups as pendants per repeat unit. In PPA, the lyotropic liquid crystalline behaviour of the homopolymer was distinctly affected by the polymerization temperature. Spectroscopic evidence strongly suggested a completely planar and ribbon-like structure, the consequence of the strong intramolecular hydrogen bonds between the OH moieties and the N atoms of the nearby benzothiazole units. The homopolymer also exhibited the unusual capability, characteristic of BBL-type ladder polymers, to form directly from its precipitate an aggregated film which displayed little or no shrinkage when dried. Anisotropic dopes of the homopolymer (dihydroxy-polybenzothiazole (PBZT)) and certain dihydroxy- PBZT/PBZT copolymers were spun into fibres with typical tensile properties for modified PBZT polymers, but marginal compressive strength (4-30ksi (l ksi=6.9 MPa) for homopolymer and 16-61ksi for the copolymers). The intrinsic conductivity for the as-spun fibre of the homopolymer was 2.2 x 10-7S cm-1 and that for heat-treated (435°C) fibre was 5.6 x 10-8 S cm-1.

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Conformational energy calculations are used to develop a rotational isomeric state (RIS) model for polystyrene including t, 9 and 0 states. No adjustment is made to match experimental data as with an earlier two-state model due to Yoon and coworkers. The three-state model correctly predicts a higher limiting characteristic ratio for the syndiotactic polymer as compared to the isotactic. It is shown how molecular dynamics simulations on a periodic cell containing polystyrene fragments in a O solvent can be used to make a systematic correction for the short-range solvent effect, enhancing the tendency of the syndiotactic chain to expand relative to the isotactic chain. After solvent correction, C~ is predicted about 26-28% too low for both isotactic and syndiotactic polystyrene, a deviation that can be attributed to other approximations inherent in the RIS method

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