Crystalline structure of poly(methyl-n-propylsilane)

The thermal behavior and physical structure of atactic poly(methyl-n-propylsilane) (PMPrS) have been investigated by complementary techniques. Temperature-dependent wide-angle X-ray scattering as well as thermal analysis clearly indicate that atactic PMPrS crystallizes below 40°C in a monoclinic lattice with PMPrS adopting an all-trans planar zigzag conformation. Above 40°C, the polymer is in the isotropic amorphous state. A restricted analysis of the structure factors of PMPrS has been performed, indicating that the zigzag planes most probably lie in (1 10) planes. The chains pack with little interpenetration, and the crystals may be considered as bundles of long, closely packed prisms. The restricted interlocking of neighboring chains results, in turn, in a poor register of the chains along the c-axis. Moreover, transmission electron microscopy reveals that the crystallized polymer adopts a lamellar microstructure, with parallel lamellae tending to form tight bundles. Both electron microscopy and small-angle X-ray scattering indicate crystal thicknesses of about 60 Å. Finally, PMPrS was found to crystallize with a nucleation-controlled type of kinetics. Avrami exponents were calculated as n ≈ 1, suggesting a fibrillar growth geometry compatible with the absence of spherulitic superstructure. A double-melting behavior is also observed for PMPrS. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 1533–1543, 1997     

Self-organization and polyolefin nucleation efficacy of 1,3:2,4-di-p-methylbenzylidene sorbitol

Recent studies have demonstrated that addition of a small quantity of dibenzylidene sorbitol (DBS) to a molten polymer may result in a physical gel if conditions permit the DBS molecules to self-organize into a three-dimensional network composed of highly connected nanofibrils. If the polymer crystallizes, DBS may also serve as a nucleating agent, promoting the formation of spherulites, especially in commercially important polyolefins such as polypropylene. We examine the thermal and mechanical properties, as well as the morphological characteristics, of an isotactic polypropylene copolymer with 3 wt % ethylene upon addition of less than 1 wt % of 1,3:2,4-di-p-methylbenzylidene sorbitol (MDBS). From dynamic rheological measurements, pronounced complex viscosity increases, attributed to MDBS nanofibril network formation, are observed at concentration-dependent temperatures above the melting point of the nucleated copolymer. Transmission electron micrographs of RuO₄-stained sections confirm the existence of MDBS nanofibrils measuring on the order of 10 nm in diameter and, at higher concentrations, fibrillar bundles measuring up to about 200 nm across and several microns in length. The addition of MDBS at different concentrations is also found to promote increases in optical clarity, yield strength, tensile strength, and ultimate elongation of modified copolymer formulations. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 2617–2628, 1997     

Layer structures. VI. Chiral sanidic polyesters derived from 2,5-bis (dodecyloxy) terephthalic acids and 4,4′-dihydroxybiphenyl

Copolycondensations of (S,S)-2,5-bis(2-methylbutyloxy) terephthaloylchloride with 2,5-bis(dodecyloxy)terephthaloylchloride and with 4,4′-bistrimethylsiloxybiphenyl yielded a series of novel chiral thermotropic copolyesters. These polyesters were characterized by elemental analyses, inherent viscosities, ¹H-NMR spectroscopy, optical rotations, optical microscopy, DSC measurements, and WAXS powder patterns recorded with synchrotron radiation under variation of the temperature. All homo- and copolyesters formed a solid sanidic layer structure with melting temperatures (T_m) ≥ 200°C. A broad enantiotropic nematic or cholesteric phase is formed above T_m with isotropization temperatures (T_is) in the range of 275–325°C. Yet, the T_m of the chiral homopolyester is so high (378°C) that the melting process is immediately followed by rapid degradation. The cholesteric phases of the copolyesters displayed unusual mobile schlieren textures, but a stable Grandjean texture was never obtained. Cholesteric domains consisting of loose bundles of more or less helical main chains are discussed as supramolecular order responsible for the observed textures and their pronounced temperature dependence. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 947–957, 1997     

Macrocyclic oligoimides. I. Preparation of macrocyclic oligoetherimides via Kricheldorf substitution polymerization

Macrocyclic oligoetherimides were synthesized by means of Kricheldorf's nucleophilic aromatic substitution polycondensation. A solution containing equimolar quantities of bis(trimethylsilyl ether) of bisphenol and arylenebis(fluorophthalimide) was continuously added into a high boiling solvent containing CsF catalyst under a pseudo-high dilution condition. The resulting reaction mixture contained a high yield of cyclic oligomers which could be isolated by solvent extraction. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 759–767, 1997     

Polyesters containing sulfur. V. Preparation and characterization of new polyester–sulfur compositions

New polyester–sulfur compositions with increased tensile strength were obtained by using new thiopolyesters crosslinkable with sulfur, derived from diphenylmethane-4,4′-di(methylthiopropionic acid) and ethanediol (E-P) or 2,2′-oxydiethanol (ODE-P). Such characteristics as hardness, tensile, thermomechanical, as well as some electrical properties were determined. The structure of these compositions was investigated by solid-state ¹³C-NMR spectroscopy. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2231–2238, 1997     

Optically active dimethylsiloxane copolymers with nucleophilic chiral sulfur groups pendant to the polysiloxane chain

Polydimethylsiloxanes with part of the siloxane units bearing an optically active sulfoxide group were synthesized. These copolymers had chiral sulfur centres connected to the siloxane chain by a dimethylene bridge. They were obtained mostly by the kinetically controlled anionic ring-opening polymerization of 1-(2-organothioethyl)1,3,3,5,5-pentamethylcyclotrisiloxanes, followed by stereoselective oxidation of prochiral groups to yield partially enantiomeric sulfoxide groups. Sulfoxides bearing cyclic monomers were also used. Polymers were characterized by spectroscopy and polarimetry. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 879–888, 1997     

Preparation of aromatic copolyamides containing regularly placed 1,6-hexamethylenediamine units

Copolyamides based on poly(m-phenylene isophthalamide) and poly-(p-phenylene terephthalamide), to which 1,6-diaminohexane units were regularly inserted every 3 or 5 phenylene monomer units, were synthesized. The copolymers were obtained by condensation of individually prepared diamino- and dicarboxylic-building blocks via the Yamazaki–;Higashi reaction. Solubility of the copolyamides are discussed in relation with the structure. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2379–2386, 1997     

Interaction of the low-molecular weight salts with cationic polyelectrolytes

The interaction of several mono-, di-, and trivalent anions with cationic polyelectrolytes having different contents in N,N-dimethyl-2-hydroxypropylen ammonium chloride units (polymer A) or tertiary amine N-atoms and PEG (polymer PEGA) in the main chain was studied by viscosimetric and conductometric measurements. Both methods have shown a stronger interaction for tri- and bi- than for univalent counterions. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 2571–2581, 1997     

Effect of quinone derivatives and sulfhydryl compounds on swelling of poly(4-vinylpyridine) gels in organic solvents

Interactions of sulfhydryl compounds and quinone derivatives with poly(4-vinylpyridine) gels have been studied. Adsorption of long-chain sulfhydryl compounds onto gels causes the gel to swell, whereas oxidation of the adsorbed sulfhydryl compound to disulfide by a quinone derivative results in the gel shrinking. The higher the donating ability of the sulfhydryl compound, the stronger its interaction with a quinone derivative and thus the faster the removal from the gels, as revealed by HPLC. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 795–798, 1997     

NMR study of the structure and properties of poly(MMA-co-VP) crosslinked hydrogels

¹H- and ¹³C-NMR techniques were used to study the microscopic structure of NMA/VP copolymer hydrogels. Evidence was obtained for a plasticization effect of MMA chains by VP. An original ¹H-NMR approach revealed the existence of several types of water with various degree of bounding to the polymer network, a conclusion that is corroborated by a complementary ¹³C-NMR study. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3619–3625, 1997     

Synthesis,polymerization, and isomerization of isoimide containing acrylate esters

Several isoimides substituted with hydroxylated substituents were prepared, and allowed to react with acryloyl chloride to form the corresponding acrylate esters. The acrylates were polymerized free radically using AIBN as the initiator yielding medium molecular weight polyacrylates. Upon warming the prepared polyacrylates or treatment with base most of the isoimide pending groups rearranged to the stable form of the corresponding imides. These rearrangements were accompanied by increase in softening points of the polymers forming thermally more stable resins. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3125–3130, 1997     

ESR study on chemical crosslinking reaction mechanisms of polyethylene using a chemical agent—II. The effect of phenolic antioxidants

The effect of antioxidant on the reaction mechanism of chemical crosslinking of polyethylene (PE) with dicumyl peroxide (DCP) at high temperatures was investigated by electron spin resonance (ESR). The antioxidant reacts with the alkyl radicals in PE formed by the thermal decomposition of DCP above 120°C, and disturbs the crosslinking. A phenolic type antioxidant produced the phenoxy radical by the reaction with alkyl radicals formed in PE. It is suggested that the selection of a suitable antioxidant for PE crosslinking can be made by ESR analysis. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2431–2439, 1997     

Synthesis and characterization of optically active polyamides derived from carbohydrate-based monomers

The synthesis of three new stereoregular AB-type polyamides based on D -ribono-1,4-lactone, L -arabinose, and D -xylose has been carried out by the active ester polycondensation method. These polyamides were characterized by elemental analysis, IR and NMR spectroscopies, and powder X-ray diffraction. They displayed optical activity and had a pronounced affinity to water, although they were not soluble in this solvent. The polyamide obtained from D -ribono-1,4-lactone was highly crystalline and yielded films with spherulitic texture. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3645–3653, 1997     

A TSC investigation of polymer–polymer contact charging

The transfer of charge across the interface between two materials brought into contact was studied by measuring the small currents produced when layered films composed of two dissimilar films were first heated and then held under isothermal conditions. It was found that, given a fixed electrode orientation, the polarity of the current generally reversed when the relative position of the films were reversed. The sense of the current was in agreement with that expected from the polymer work functions. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2901–2912, 1997     

Further studies of end groups derived from benzoyl peroxide

There has been a suggestion that, for polymerizations initiated by benzoyl peroxide, the use of benzene as diluent may cause uncertainties about the conclusions reached from studies of the end groups in the resulting polymers. It is now shown that no substantial changes are caused by the replacement of benzene by other solvents. This finding contributes to the conclusion that any capture of benzoyloxy radicals by benzene is only transitory and does not invalidate the deductions made from the results of analyses of polymers for benzoate and phenyl end groups derived from the peroxide. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2955–2960, 1997     

Cationic polymerization of diglycidyl ether of Bisphenol A. II. theory

Network formation in cationic polymerization of polyepoxides was treated using a combination of kinetic theory and the statistical theory of branching processes (TBP). The complex reaction mechanism involved a degradative termination reaction affecting the molecular weight distribution of the primary chains. Moreover, formation of low-molecular-weight products, initiation, two mechanisms of propagation and transfer were taken into account. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 651–663, 1997     

Hypercritically enhanced distortion of a phase diagram: The (polystyrene + acetaldehyde) system

We report new experimental evidence of the existence of double critical points in a binary system. Pressure-temperature data on the solubility of (polystyrene + acetaldehyde) were obtained using a low-angle light-scattering technique. Phase diagrams change from an UCST/LCST configuration showing a marked double maxima to an hour-glass shape with a “window of miscibility” as pressure decreases. Successful modeling of these unusual shapes was achieved by using a computation algorithm which incorporates a temperature- and concentration-dependent interaction parameter. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys, 35: 631–637, 1997     

Multidimensional benzobisoxazole rigid-rod polymers. I. Preparation and characterization

Two- and three-dimensional rigid-rod polymers containing benzobisoxazole structures were prepared through the polycondensation in polyphosphoric acid of 4-[5-amino-6-hydroxybenzoxazol-2-yl]benzoic acid (ABA) with trimesic acid and 1,3,5,7-tetrakis(4-carboxylatophenyl)adamantane, respectively. Thermal properties of the polymers were determined by differential scanning calorimetry, thermogravimetric/mass spectral analysis, and isothermal aging studies. The multidimensional polymers exhibited lower solution viscosities and lower thermooxidative stabilities than the one-dimensional polymer generated by the homopolymerization of ABA under identical reaction conditions. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 3451–3456, 1997     

Polyepichlorohydrine stabilized core shell microspheres by dispersion polymerization

Polystyrene microspheres ranging in diameter from 2 to 10 μm were prepared by dispersion polymerization in the presence of polyepichlorohydrine as the steric stabilizer precursor in alcoholic media. To clarify the effects of the solvent mixture composition, initiator concentration and steric stabilizer amount on the microsphere characteristics, including the molar mass parameters of the polymeric material, the microsphere size, and the steric stabilizer surface density, a three-factor full factorial design involving two levels of each of the factors and replicate experiments was employed. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 681–688, 1997     

Copolymers of (±)2-ethylhexyl acrylate and 3-[3,3,3-trimethyl-1,1-bis (trimethylsiloxy) disiloxanyl] propyl methacrylate

Statistical copolymers of (±)2-ethylhexyl acrylate and 3-[3,3,3-trimethyl- 1,1-bis (trimethylsiloxy) disiloxanyl] propyl methacrylate were synthesized and the reactivity ratios and the Q and e values were calculated. The glass transition temperatures of the copolymers were in good agreement with the predictions of Fox's equation and Wood's formula. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 3571–3574, 1997