NMR studies of conformations and dynamic processes—III : Cyclophanes with unsaturated bridges

Three cyclophanes, each displaying a different type of dynamic process, have been studied by NMR methods. The barriers to these processes are attributed mainly to the decrease in π-electron overlap between the benzene rings and adjacent double bonds which occurs in the transition state for each process. In [5₂] paracyclophanetetraene, two successive flippings of the benzene rings interconvert the two hydrogens in the methylene groups (Scheme 1). In tetramethyl [2₄] paracyclophanetetraene, the passage of one methyl group through the central cavity of the molecule interconverts two conformations of similar, but not equal, free energy (Scheme 2). In [2₆] orthoparacyclophanehexaene, the orthosubstituted rings change sides by passing through the centre of the cyclophane (Scheme 3).     

Photo-oxidation of polystyrene—Part 3. Photo-oxidation of 2-phenyl butane as model compound for polystyrene

During the photo-oxidation of 2-phenyl butane as model compound for polystyrene the following compounds were isolated and identified: acetophenone, propiophenone, 2-phenyl-2-butanol, 2-phenyl-2-hydroxy-(3,4) butene, 2-hydroxy-acetophenone, 2-hydroxy-propiophenone; o-methyl (methyl-benzoate), 1-keto-1(2) hydroxy butyl-(2,4)hexadienoic acid methyl ester and 1-(2)hydroxy butyl-2-keto-butyrolactone.Mechanisms for the formation of these compounds have been proposed. Comparison of carbonyl group frequencies in the products of photo-oxidised 2-phenyl butane with corresponding frequencies in photo-oxidised polystyrene gives evidence of similar mechanisms of photo-oxidation.     

Improved matrix-assisted laser desorption/ionisation sample preparation of a partially depolymerised cellulose derivative by continuous spray deposition and interfacing with size-exclusion chromatography

Continuous spray deposition (CSD) of aqueous solutions of partially depolymerised methyl cellulose was found to improve matrix-assisted laser desorption/ionisation (MALDI) sample preparation. One feature was that the sensitivity in MALDI time-of-flight mass spectrometry increased up to an order of magnitude compared with the standard sample preparation method. Another feature was that CSD provided targets for MALDI with homogeneously distributed analyte. This resulted in a more even signal intensity and a higher reproducibility than in the standard method. High-mass discrimination was more pronounced in CSD than in the standard method. Size-exclusion chromatography with aqueous eluent was coupled online to CSD onto matrix-precoated foils. The suitability for determination of the molar mass distribution of methyl cellulose was investigated.     

Amphiphilic segmented polyurethanes as surface modifying additives

Amphiphilic segmented polyetherurethanes were prepared from methylene diphenylene diisocyanate (MDI), poly(ethylene glycol) 1500 (PEG), and a fatty acid monoglyceride as a chain extender. The polymers were not soluble in water or methanol, but dissolved readily in organic solvents. The amphiphilic properties were demonstrated as a large hysteresis in the water contact angles, exceeding 110°. The amphiphilic polymers were shown to modify the surface properties of a poly(ether urethane) (PEU) and a poly(ether urethane urea) (PEUU) when added in 1–10 wt %, presumably due to migration of the additive to the surface. The surfaces of particularly the PEU blends became highly amphiphilic, exhibiting contact angles hystereses up to 90–100°. A surface saturation effect was observed at 5% added amphiphilic polymer. A difference in the behavior of PEU and PEUU was ascribed to differences in solubility of the additive in the matrix. On long-term exposure to water the PEUU blends increased their amphiphilic behavior.     

“Surface-photografting”: new applications to synthetic fibers

“Surface-photografting” with UV-irradiation of polypropylene (PP) fiber and film and high-strength polyethylene (HSPE) yarn has been made with acrylic acid (AA) and acrylamide (AM) as monomers and benzophenone (BP), 4-chlorobenzophenone (4-BCP) and hydroxylcyclohexylacetophenone (HHA) as photoinitiators using a new continuous method. The grafting reaction occurs in a thin liquid layer on the fiber or film substrate, which is presoaked in a solution containing initiator and monomer. After irradiation with a highpressure mercury lamp, HPM 15 (2 kW) from Philips, for 5–20 sec at about 50°C the fiber and film surface is completely covered with a 2–8 nm thick layer of grafted polymer, analyzed by electron spectroscopy for chemical analysis. The grafting efficiency is 70–80%, i.e. only 20–30% of the polymer is homopolymer which can be removed by extraction. The grafted layers are so thin that they cannot be analyzed as weight increase (<0.1% of fiber weight). Absolute values for the amount of grafted AA polymer is analyzed by microtitration of the COOH groups at the fiber surface. The results agree well with the relative ESCA values. Grafting of commercial PP yarn with AA increases the adsorption of Crystal Violet dye with a factor of about 6. Grafting the same yarn with AM increases the adhesion to epoxy resin by a factor of 3–4 without affecting the mechanical properties of the fiber more than a few percent. For comparison, strips of blown PP film (5 mm wide) are modified by “surface-photografting” with AM. With increasing grafting, the contact angle for drops of distilled water decreases from 90° to 20°, indicating extensive wetting. The adhesion to epoxy resin increases from about 0.35 to 1.7 N/mm², i.e. with a factor of about 5 when the film surface is completely covered. Other comparisons are made with grafting of commercial HSPE yarn. Grafting with AA increases the adsorption of Crystal Violet dye by a factor of about 6. Grafting with AM increases the adhesion to epoxy resin from 0.25 to 1.3 N/nm², i.e. with a factor of 5. The bulk mechanical properties of the HSPE filaments are not affected by the grafting measured as tensile strength 2.7±0.1 GPa, elongation at break 4.8±0.3%, and Young's modulus 55±3 GPa, both before and after “surface-photografting”.     

Determination of dynamic and sliding friction, and observation of stick-slip phenomenon on compacted polymer powders during high-velocity compaction

Dynamic friction, sliding friction, and the stick-slip phenomenon have been studied on compacted polymer powders during high-velocity compaction. It is particularly important from a practical point of view to distinguish the stick-slip mechanism and the sliding mechanism which occur concurrently. A practical experimental system has been successfully developed to study the dry frictional force and to measure the sliding coefficient between the polymer powder particles and the die wall during high-velocity compaction. Two new components have been introduced as relaxation assists to improve the compaction process by reducing the frictional forces. It was found that the relaxation assist device leads to an improvement in the polymer powder compaction process by giving a more homogeneous opposite velocity and a better locking of the powder bed in the compacted form with less change in dimensions. The subsequent movement of the particles can be reduced and the powder bed attains a higher density with a minimum total elastic spring-back. The relative time of the stick-slip phenomenon during the compacting stage is also reduced so that the time needed to transfer from an intermittent stick-slip state to a smooth sliding state is reduced and the powder bed slides smoothly. It was found that the dynamic, dry frictional force is intermittent (stick-slip mechanism) at low compaction rates but that at high compaction rates is becomes more smooth (sliding mechanism). Both mechanisms depend on the nature of the powder and on the compaction conditions. At the beginning of the compaction stage, the sliding coefficient decreases due to an increase in the radial to axial stress ratio until the maximum pressure has been reached. During the reorganization stage, more time is needed for large particles to move, rotate and slide due to their relatively large diameter and mass. As a result, the reorganization stage is extended and the stick-slip phenomenon is observed more with increasing particle size. Much better transfer of the pressure throughout the powder bed and less loss of pressure lead to a higher sliding coefficient due to the overall friction during the compaction process. It was found that the sliding coefficient is proportional to the density.

A more homogeneous density distribution in the compacted powder and a smaller pressure loss during compaction has a major influence on the sliding coefficient and on the quality of the compacted material.     

Amphiphilic comb-shaped polymers from poly(ethylene glycol) macromonomers

Comb-shaped amphiphilic graft copolymers composed of hydrophobic backbones and hydrophilic side chains were prepared by radical copolymerization of poly(ethylene glycol) monomethacrylate macromonomers, and methacrylate and acrylate comonomers in toluene. The copolymerizations were very sensitive to the reaction conditions, and insoluble cross-linked gels were easily formed. The yields of soluble copolymers were affected by the initiator concentration, the macromonomer concentration, and the choice of chain transfer agents and comonomers. Solubilities of the copolymers in water or methanol were found to depend on the sizes and the numbers of the PEG side chains. The copolymers showed surface activity with CMC:s in the order of 0.1–1.5 g/L and surface tensions of 36–56 dyn/cm. When tested as emulsifiers most of the copolymers gave oil-in-water type emulsions at room temperature. Polymers carrying MPEG 2000 side chains were crystalline with melting points of 38–44°C, while those based on PEG 400 and 1000 were mostly amorphous with glass transition temperatures between -55 and -60°C. © 1992 John Wiley & Sons, Inc.     

ESR studies of methallyl monomers with redox systems

The effects of three types of free radical initiators (HO·, H₂N·, and H₃C·) from redox systems, have been studied for four types of methallyl monomers, by use of ESR with a flow system. The structure, the relative concentrations, and the steric conformations of the monomer radical intermediates have been derived from the ESR spectra. In the case of H₂N · and HO · addition to methallyl alcohol (MAA), methallyl amine (MAAm), and sodium methallyl sulfonate (SMAS), the ESR spectra of the reacting species are interpreted as monomer head radicals only (H₂N · and HO · are added to the monomer tail). Methallyl acetate (MAAc) with HO ·, is an exception, giving hydrogen abstraction to form an allyl type radical. This reaction may influence the polymerization behavior of MAAc. The methallyl monomers behave differently from the allyl monomers, where appreciable amounts of monomer tail radicals were found in addition to the head radicals which were the main species. For methallyl monomers, this may be due to steric hindrance caused by the two substituents on the α carbon. The CH₃ radicals add only to positively polarized reactive double bonds, i.e., in SMAS in this study, and allyl alcohol in a previous study. The coupling constants of β CH₂ protons vary considerably with the substituents. For β₁ protons, the coupling constants decrease in the order OH > CH₃ > NH₂. For β₂ protons (allyl hydrogen), the coupling constants decrease in the order CH₂OH > CH₂NH₂ > CH₂OCOCH₃Na, i.e., the constants decrease in the order of increased bulkiness of the groups. Some exceptions are interpreted as due to complex formation with Ti⁴⁺. The effects of pH of the reaction medium are largely those expected.     

Preparation and properties of alkylated poly(styrene-graft-ethylene oxide)

Poly(styrene-graft-ethylene oxide), having alkyl chains (C₁₂ or C₁₈) on the polystyrene main chain or on the poly(ethylene oxide) (PEO) side chains, were synthesized. The main chain was alkylated by first ionizing amide groups in a styrene/acrylamide copolymer with tert-butoxide, and then using the amide anions as sites for reactions with 1-bromoalkanes. An excess of amide anions was used in the reaction, and the remaining anions were subsequently utilized as initiator sites for the anionic polymerization of ethylene oxide (EO). Synthesis of poly(styrene-graft-ethylene oxide) with alkylated side chains was accomplished by polymerization of EO onto the ionized styrene/acrylamide copolymer, followed by an alkylation of the terminal alkoxide anions with 1-bromoalkanes. The alkylated graft copolymers were structurally characterized by using elemental analysis, ¹H NMR, GPC, and IR spectroscopy. DSC analysis showed that only graft copolymers with PEO contents exceeding about 50 wt % and side chain crystallinities comparable to those of homo-PEO. Main chain alkylated graft copolymers generally had higher crystalinities, as compared to nonalkylated and side chain alkylated samples. The graft copolymers absorbed water corresponding to one water molecule per EO unit at low PEO contents. The water absorption increased progressively at PEO contents above 30 wt % for main chain alkylated samples and above 50 wt % for non-alkylated samples. © 1995 John Wiley & Sons, Inc.     

THE ROLE OF SINGLET OXYGEN IN THE PHOTOOXIDATION OF POLYMERS

Abstract— This paper is a critical review of the singlet oxygen oxidation of polymers in solid state and in solution, referring in particular to polydienes, polystyrene and polyvinyl chloride). The singlet oxygenation of polydienes resulted in formation of allylic hydroperoxide groups with shifted double bonds, according to the "ene"-type process. The singlet oxygenation of polystyrene and polyvinyl chloride) occurs only when the new double bonds are formed in these polymers. During dye-photosensitized singlet oxygenation of polydienes in methanol-benzene solution, a very rapid decrease in the molecular weight was observed. For the chain-scission which occurs, not only singlet oxygen but several intermediates such as radicals, bi-radicals and cation-radicals which are formed during light fading of dyes are responsible. At the end of this paper a short review appears which has been focused on the quenching behavior of stabilizers, particularly interactions with singlet oxygen.