The effect of residual acetate groups on the structure and properties of vinyl alcohol–ethylene copolymers

Vinyl alcohol–ethylene (VAE) copolymers, commercially manufactured by hydrolysis of the corresponding vinyl acetate–ethylene copolymers, can contain small amounts of unhydrolyzed vinyl acetate. This article shows the influence of these residual groups on the structure of the resulting copolymers, studied by nuclear magnetic resonance and wide‐angle X‐ray scattering. Thermal and mechanical properties of these materials were investigated by differential scanning calorimetry, thermogravimetry, drawing behavior, birefringence measurements, and dynamic mechanical analysis. The structure of the copolymers is considerably affected by the volume of the residual acetate groups, bigger than that of the hydroxyl ones, which hinders the crystallization process. In relation to the thermal and mechanical properties, the temperature and enthalpy of melting as well as the Young's modulus and yield stress, decrease as vinyl acetate molar fraction increases. Moreover, the α and β relaxations are shifted to lower temperatures as residual content in the copolymer is raised. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 573–583, 2000     

Adhesive properties of ethylene and vinyl acetate copolymers

Surface properties of ethylene and vinyl acetate copolymers (EVAs) are considered depending on their composition and history of surface formation. The kinetics of structural transformations in the near-surface layers of copolymers is investigated. Relaxation times and the equilibrium state of the EVA surface are determined. The orrelation dependence between the surface energy of copolymers and their adhesive properties for substrates of different natures is constructed.     

The effect of molecular weight and crystallite structure on yielding in ethylene copolymers

Nominal stress-strain curves of a series of random ethylene-hexene copolymers having narrow composition and most probable molecular weight distributions were investigated. A series of such molecular weight copolymers with a constant concentration of branches were crystallized under a variety of conditions. In each molecular weight series the level of crystallinity was approximately constant. Particular attention was focused on the yield region and the nature of the yielding process. It was found, quite surprisingly, that the yield stress was not solely dependent on the crystallinity level. Moreover, the shape of the force-elongation curve in the yield region was very dependent on the molecular weight and the crystallization mode. These changes in yielding correlated quite well with the overall crystallite structure that was characterized by thin section transmission electron microscopy. The orthorhombic unit cell of polyethylene was maintained in all the samples despite the changes that occurred in the overall crystallite structure. © 1997 John Wiley & Sons, Inc.     

Adhesive properties of binary mixtures of some ethylene copolymers

It is shown using the example of polyolefin thermoplasts that the value of adhesion strength is determined by the mechanical properties of a composition.     

Oxygen‐barrier properties of copolymers based on ethylene terephthalate

The oxygen‐barrier properties of amorphous polyethylene terephthalate‐based copolymers with various acid comonomers were examined. The incorporation of increasing amounts of isophthalate, phthalate, or naphthalate gradually reduced the permeability P toward the low values obtained for the corresponding homopolymers. The permeability of poly(ethylene 3,4′‐bibenzoate) homopolymer was only slightly lower than that of polyethylene terephthalate, and the copolymers correspondingly exhibited a very gradual decrease in P as the amount of 3,4′‐bibenzoate (3,4′BB) increased. In contrast, copolymerization with the linear isomer, 4,4′BB, produced a substantial increase in P. Generally, comonomer affected the solubility S less than the diffusivity D, and therefore changes in P reflected primarily changes in D for the polymers studied. The diffusivity and solubility depended on the copolymer composition in accordance with static and dynamic free‐volume concepts of gas permeability in glassy polymers. The solubility S correlated with the amount of free volume as determined by the glass‐transition temperature. Correlation of the diffusivity D with the magnitude of the subambient γ relaxation identified dynamic free volume with thermally activated conformational changes and segmental motions. Correspondence in the activation energy confirmed the relationship. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1889–1899, 2001     

Surface properties of styrene–ethylene oxide block copolymers

Hydrophobic–hydrophilic block copolymers were prepared by “living” anionic polymerization. They consist of polystyrene and poly(ethylene oxide) blocks, and are soluble in water. Their interfacial properties were investigated, employing aqueous solutions. The block copolymers lowered the surface tension of water in analogy with the low molecular weight surfactants such as sodium lauryl sulfate and heptaethylene oxide n-dodecyl ether. Their aqueous solutions exhibited solubilization properties differing from those of polyethylene glycol. Therefore, it is thought that the polystyrene blocks produce solubilization phenomena. In samples of the same styrene content, the precipitation temperature of a high molecular weight copolymer in water was lower than that of a low molecular weight copolymer at the same concentration in the same solvent. The surface tension and precipitation temperature of aqueous solutions seem to be influenced by molecular weight and composition.     

The crystallization characteristics of ethylene block copolymers

Block copolymers of ethylene and butadiene with short ethylene sequences and degrees of polymerization up to 250 have been studied calorimetrically to determine their structure in the melt and also on crystallization. Crystallization rate characteristics and the thermodynamic parameters of the melting of block copolymers were studied. Block copolymers with ethylene sequences with degrees of polymerization below 20–30 were amorphous. Those with ethylene sequences of 35–45 units crystallized with extended chain crystals; above 45 units the polyethylene blocks crystallized with chain folding. There was a corresponding reduction in the melting point of the crystals and in the surface free energy of the crystals. The extent of crystallinity that developed within the copolymers was dependent on crystallization temperature and independent of time. This behavior was unlike that exhibited by polyethylene samples of similar molecular weight and was considered due to the effect of phase separation of the two blocks in the melt and nucleation control of the crystallization of the isolated domains. Analogous behavior was observed with polyethylene for polymer blends with polystyrene.     

Synthesis of ethylene copolymers

Summary Copolymers of ethylene with styrene, methyl methacrylate, acrylonitrile, and vinyl acetate were prepared by reaction in toluene in presence of tributylborine as polymerization catalyst.     

Dynamic mechanical properties of homogeneous copolymers of ethylene and 1-alkenes

The dynamic mechanical properties of homogeneous copolymers of ethylene with 1-butene, 1-octene, and 1-octadecene prepared by means of a vanadium-based catalyst system have been determined. The 1-butene copolymers show α′ and α transitions in the 20–60°C temperature range, whereas the 1-octene and 1-octadecene copolymers show single α transitions. The intensity of the β transition increases with comonomer content in 1-butene and 1-octene copolymers and also with the amount of interfacial material present. In ethylene-1-octadecene copolymers, this intensity is comparatively low, even though there is about 20% interfacial material present. The implications of these results with regard to the nature of interfacial material are discussed.     

Substituents effect on the properties of sulfonated polyimide copolymers

A series of sulfonated polyimide (SPI) copolymers containing methyl, methoxy, or fluorine groups were synthesized to elucidate the substituents effect on their proton conducting properties as well as thermal, hydrolytic, and oxidative stability for polymer electrolyte membrane fuel cell applications. SPIs of high molecular weight (M_w > 200 kDa, M_n > 80 kDa) along with the ion exchange capacity (IEC) varying between 1.34 and 1.91 mequiv/g were obtained, which gave tough, ductile, and flexible membranes by solution casting. The thermal properties of the SPIs were dominated by the electronic structure of the sulfonated aromatic rings. The electron‐donating methyl groups lowered the thermal decomposition temperature. The hydrolytic and oxidative stability was roughly in the order of IEC (the higher IEC membranes were less stable). Fluorine groups, either as ? F or ? CF₃, had negative effect on the hydrolytic and oxidative stability. In the water uptake and proton conductivity, hydrophobic components are rather more influential than the substituents. It was found out that the SPI(5, 8, 0.7) containing bis(phenoxy)biphenylene sulfone moieties as a rigid hydrophobic component showed the best balanced properties in terms of the stability and the proton conductivity for its rather low IEC. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4469–4478, 2008     

The environmental stress cracking of linear ethylene copolymers

A new method of measuring the environmental stress cracking (ESC) of polymers at constant strain is proposed in which an occurrence of fracture is detected automatically. The new method showed a very good reproducibility within 10% compared with a few hundred percent by conventional methods. The ESC values obtained by the new method was found to be proportional to those by the conventional Bell Telephone Laboratory method in which the ESC was determined by the occurrence of small cracks, with a proportionality contant of 2.8. From the fact that the difference of both ESCs were also proportional to the ESC determined by the BTL method, it was concluded that the value of the ESC was proportional to the velocity of crack propagation. These conclusions were supported by the observation of the test pieces by a scanning electron microscope. The study of the blended polymers revealed that the additivity of logarithmical ESC with weight fraction holds for a wide range of polymes, which enables estimation of ESCs up to millions of hours. Using this technique, the ESCs of a wide range of molecular weights and a number of short chain branches were studied. It was found that the branches in the high molecular weight polymer were much more effective on the ESC than those in the low molecular weight polymer. This makes it possible to design a good resin with a good ESC.     

The effect of aminoalkoxy and glycidoxyalkoxy silanes on adhesion characteristics of double and triple copolymers of ethylene

The effect of aminoalkoxy and glycidoxyalkoxy silanes on strength of a polyethylene-modified copolymer-metal (polyethylene terephthalate) adhesion joint was studied for double and triple acetate copolymers of ethylene. It was shown that such modification resulted in an essential increase in the deformation-strength and adhesion characteristics of adhesive joints.     

The effect of annealing on the structure and relaxation processes of vinyl alcohol–ethylene copolymers

An annealing process has been applied to three samples of vinyl alcohol–ethylene (VAE) copolymers, richer in the former comonomer. The effect of such a process on the structure and on the relaxation mechanisms is studied. The structure of the three VAE copolymers has changed slightly. Nevertheless, the viscoelastic relaxation processes have been significantly affected for the thermal treatment. Two additional relaxations have appeared: one of them at temperatures above the relaxation associated to the glass transition, and the other at temperatures below the β mechanism of these copolymers. The temperature location, intensity, and apparent activation energy of the distinct relaxations found are discussed and compared with those in the original copolymers and the homopolymers, poly(vinyl alcohol) and polyethylene. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 1–12, 2001     

The influence of an organosilicon modifier on the properties of a compound based on epoxy-urethane oligomer

To improve the performance characteristics of products made of highly-filled polymer compositions, modification of a compound based on epoxy-urethane oligomer was performed. The SH 198 amino functional organosilicon oligomer was used as a modifier. The performed studies established that an organosilicon modifier increases the gel time and the curing time of the composition based on epoxy-urethane oligomer, shows the plasticizing effect on a compound, decreases its glass transition temperature from 16.5 to 9°C, and increases the deformation in the temperature range of from–40 to +50°C.     

Syntheses and properties of ethylene sulphide-isobutylene sulphide copolymers and their unsaturated terpolymers

The synthesis with anionic catalysts and the characterization of ESIBS copolymer and ESIBSATE terpolymer are reported (ES, IBS, ATE and PS = ethylene sulphide, isobutylene sulphide, 3-allyloxy-1,2-epithiopropane and propylene sulphide respectively). For ESIBS copolymer with 35–55% ES, nearly amorphous structures, were obtained. Microstructures, investigated by ¹³C-NMR, have been compared with that of the ESPS copolymer; the ESIBS copolymer has greater blockiness than ESPS. Some preliminary results on the properties of ESIBSATE unsaturated terpolymer are also reported and compared with those of the known ESPSATE terpolymer. The good swelling values shown by the former are related to the possibility of obtaining amorphous structures with a high ES content.     

Synthesis and properties of siloxane(ethylene oxide)urethane block copolymers

A new approach to the synthesis of hydrolytically stable dimethylsiloxane-ethylene oxide polyblock copolymers is described, in which ethylene oxide and siloxane blocks are linked by urethane groups. The molecular-mass parameters of block copolymers of different compositions are determined by capillary viscometry, light scattering, and gel-permeation chromatography. The temperature transitions in copolymers are characterized by differential scanning calorimetry.     

The effect of the composition on the properties ofγ-irradiated ethylenevinyl alcohol copolymers

Two ethylene-vinyl alcohol copolymers (Eval E and Eval F with about 45% and 25% of ethylene respectively) have been irradiated in air in the dose range 0–200 Mrad. The irradiated samples show both crosslinking and degradation; the former effect is more relevant in the copolymer with a larger content of polyethylene. Calorimetric results show that both the crystalline and the amorphous phases are involved in the reactions initiated by the irradiation.     

The effect of the composition on the properties of γ-irradiated ethylenvinyl alcohol copolymers

Stress-strain and dynamic-mechanical tests were performed on two ethylene-vinyl alcohol copolymers (Eval E and Eval F, with about 45% and 25% of ethylene respectively) irradiated in air. The experimental results, in agreement with the solubility and calorimetric results previously reported [1], show that both crosslinking and chain scission are present, and that a decrease in the degree of crystallinity with the irradiation dose occurs.     

Thermal properties of ethylene/long chain α-olefin copolymers produced by metallocenes

Metallocene type copolymers of ethylene with the α-olefins 1-octene, 1-tetradecene and 1-octadecene were characterized by dynamic scanning calorimeter (DSC) and by dynamic mechanical analysis (DMA). At a similar comonomer content above 3 mol%, the higher α-olefins gave lower melting points, crystallinities and densities than 1-octene. In DSC a separation technique sorting the crystalline sequence lengths of the polymer into groups was applied, and DSC index, DI, which gave a semiquantitative idea of the chemical homogeneity of the comonomer compositional distributions. By DMA the storage modulus as an indicator of stiffness and loss modulus and loss tangent as a measure of the effect of branching on the β relaxations were studied. The DMA measurements showed the loss modulus maximum to be a more sensitive value than the loss tangent maximum for the characterization of the comonomer distribution. The intensity of the β transition of 1-octadecene did not increase with increasing branching in contrast to the situation for 1-octene and 1-tetradecene copolymers.     

Conformational and packing energy calculations on ethylene copolymers

A conformational analysis was performed on the isolated chains of ethylene-propene and ethylene-1-butene copolymers. The lowest energy conformations in accordance with the chain repeating distance of polyethylene were used in packing energy calculations. The results of our calculations suggest that both methyl and ethyl groups are tolerated in the crystalline conformation of a single polyethylene chain, but only the methyl group is acceptable in the crystalline state if the packing energies and the lattice deformations are taken into account.