Structure-mechanical property relationships in ethylene methacrylic acid copolymers and their salts

A dynamic mechanical study has been made of an ethylenemethacrylic acid copolymer containing 4.1 mole per cent of methacrylic acid units and its sodium, lithium and calcium salts. On the basis of the results and related physical chemical studies it is proposed that the structures of the ionized copolymers consist of three distinct phases—a crystalline polyethylene phase, an amorphous polyethylene phase, and an ionic phase consisting of ionic domains. It is further proposed that the unionized acid copolymer consists of two phases—a crystalline polyethylene phase and an amorphous phase consisting of polyethylene crosslined with hydrogen bonded, carboxylic acid dimers.     

Characterization of crosslinked ethylene—Vinylacetate copolymers

Two types of ethylene-vinylacetate copolymers, containing 16% and 9% of vinylacetate, respectively, were crosslinked with dicumyl peroxide in a Brabender plastograf. The time of the torque maximum was proportional to the degree of crosslinking. The degree of crosslinking was determined by extraction and depended on the concentration of the crosslinking agent and of vinylacetate in the copolymer, and on the crosslinking temperature and time. It was found by DSC and by solid-state CP-MAS ¹³C NMR that with the progress of crosslinking the crystalline phase of the copolymers changed to the amorphous phase. Crosslinking took place mostly on the acetate groups.     

Infrared study on methyl methacrylate-methacrylic acid copolymers and their sodium salts

Near, mid and far infrared spectra have been recorded for methyl methacrylate-methacrylic acid copolymers and their sodium salts. Methyl methacrylate-methacrylic acid copolymers, with various methacrylic acid contents were prepared by free radical polymerization. The sodium salts of (methyl methacrylate-methacrylic acid) copolymers were prepared by reaction of methacrylic acid units with sodium hydroxide. The acid content in copolymers was estimated by calorimetry and by reactivity ratios of monomers. The results showed that sodium MMA-MAA copolymers prepared by neutralization form ionic clusters and retain in its backbone non-neutralized acid groups. The results showed the effect of composition on spectroscopic data. The absorption/retention of water was observed in the examined samples.     

Dielectric and dynamic mechanical relaxation studies of styrene-acrylonitrile copolymers

Dynamic mechanical measurements (～1 Hz) and dielectric measurements (10^?4 to 10⁵ Hz) are presented for styrene-acrylonitrile copolymers containing 25 and 32.5% acrylonitrile. Two dielectric (α, β) and one mechanical (α) processes were observed and their mechanisms are discussed. It is shown that the Montrose-Litovitz fluctuation theory and Phillips-Barlow-Lamb defect-diffusion theory give reasonable representations of the dielectric α relaxation process.     

Dielectric studies of an ethylene/methacrylic acid copolymer

More extensive data over a generally wider frequency range are presented for dielectric absorption and dispersion in a specimen of an ethylene/methacrylic acid copolymer. The results are interpreted in terms of four distinct processes, two of which (the ‘β′’ and ‘γ’ processes) have now been more thoroughly and accurately characterised, and the remaining two, ascribed respectively to an electronic mechanism (A) and the presence of water (w), have not previously been reported. For the ‘β′’, ‘γ’ and ‘w’ processes, activation energies, permittivity “steps” and values of Nμ² are quoted. Agreement of measured Nμ² values with those calculated is quite good but can be made better still by assuming that > CO groups, formed by the partial oxidation of the methylene sequences, are present at a plausible concentration.     

Dielectric relaxation studies on polymeric salts: Poly(methylmethacrylate-co-N,N-dimethylaminopropyl-acrylamide) benzoic acid systems

A series of polymeric salts of p-substituted benzoic acids in poly(methylmethacrylate-co-N,N-dimethylaminopropylacrylamide) were prepared and AC impedance studies of film-attached electrodes were carried out. The impedance curves and conductivity variation with temperature were analysed. The parameter which describes the shape of the circular arcs in the impedance curves was temperature independent, and the distribution of relaxation times remained constant during the test on the material. Furthermore, the ionic conductivity was highly dependent on the chemical structure produced by the substituted benzoic group.     

Nuclear magnetic proton relaxation studies of oxidized coals

Coals of NCB rank 301 a (coking), 502 (caking) and 802 (very weakly caking) are oxidized in air at 373 K or 383 K for up to 42 days. Spin-lattice and spin-spin relaxation times, T₁ and T₂ respectively, of oxidized coals are measured using a Bruker SXP 4–100 and FT spectrometer. Free radical concentrations in the coals are obtained using a JES PE e.s.r. spectrometer. Infrared spectra of oxidized coals are obtained and optical textures of cokes from fresh and oxidized coals are assessed by optical microscopy. For two coking coals, decreasing values of T₁, and increasing concentration of free radicals occurred with oxidation at 383 K to 16 and 28 days. Thereupon values of T₁, increased and free radical concentrations decreased with further progressive oxidation. At the point of inflexion in properties, resultant cokes from the coals ceased to shown any anisotropy in their optical textures and became isotropic resembling cokes from low-rank coals. For the caking coals, T₁ increased at all stages of oxidation to 42 days with decreasing concentrations of free radicals. Two values of T₂ were found in each coal corresponding to a rigid and mobile component ((T₂)_r < (T₂)_m). The rigid component (T₂)_r was not affected by oxidation but values of (T₂)_m decreased with increasing duration of oxidation. It is considered that coking and caking coals exhibit different effects of oxidation with perhaps phenols and quinones in caking coals acting as inhibitors to the growth of stable free radicals. Oxidized coking coal may behave like fresh caking coal.     

Nitric acid digestion and crystallinity of ethylene–vinyl acetate copolymers

Nitric acid digestion studies of ethylene–vinyl acetate copolymers indicated that copolymers containing identical amounts of vinyl acetate but varying in melt index differed in crystallinity. These results were confirmed by x-ray analysis. The differences in crystallinity were interpreted as showing a variation in the degree of short-chain branching in the polyethylene segments of the copolymer chain. This variation was correlated with the conditions of synthesis.     

Study of elastic and thermoelastic properties of ethylene–propylene and ethylene–vinyl acetate copolymers. II. Thermoelastic properties

The thermoelastic properties of ethylene–propylene and ethylene–vinyl acetate copolymers crosslinked to different degrees were studied. An equation was proposed for calculating the relative contribution of the internal energy, f_U/f, from the temperature dependence of shear modulus G. Analysis of a relation for calculating f_U/f derived on the basis of the Mooney-Rivlin equation was made.     

Rheological properties of partially hydrolyzed ethylene–vinyl acetate copolymers

Studies have been made of steady-shear and dynamic viscosities for melts of two ethylene–vinyl acetate copolymers and their partially hydrolyzed derivatives using a Weissenberg rheogoniometer over the temperature range of 123–150°C with some tests at 160°C. The flow activation energy of all samples studied was essentially independent of shear stress. The introduction of hydroxyl groups in controlled concentrations, however, produced a complicated flow behavior. At low concentrations, there is a marked increase in Newtonian viscosity, flow activation energy, and shear dependence of viscosity. In contrast to previous reports, a further increase in all three functions was not observed with increasing vinyl alcohol concentration. Dynamic viscosities, in contrast, show monotonic increases with increasing hydroxyl group content, as do activation energies derived from the temperature dependence of the dynamic viscosity. These data may result from an increased chain cohesion due to hydrogen bonding of hydroxyl groups.     

Study of elastic and thermoelastic properties of ethylene–propylene and ethylene–vinyl acetate copolymers. I. Elastic properties

The elastic properties of ethylene–propylene and ethylene–vinyl acetate copolymers crosslinked to different degrees were studied. A correction of the front factor with respect to temperature has been proposed for calculation of the concentration of network chains from shear modulus G. Deviations from the Gaussian approximation of the dependence of force on deformation were evaluated.     

Effect of organic amine type on the structure and properties of the complex Zn(II) salts of ethylene–methacrylic acid copolymer with organic amines

The complex Zn(II) salts of ethylene–methacrylic acid copolymer (EMAA) were synthesized by using various organic amines from monoamines to polyamines, from primary amines to tertiary amines, and from molecular amines to polymer amines. Thermal analyses by differential scanning calorimetry (DSC), and the measurement of stiffness, melt flow rate (MFR), and dielectric properties were employed for the complex salts. It was found that the valence, strength of base, rigidity and flexibility, and bulkiness of the organic amines affect the degree of crystalline order of the ionic crystallites, which governs the stiffness of the complex ion ionomers. The stiffness is higher for the complex salts which form the higher orderliness in the ionic aggregates. The organic amines with two or more primary aliphatic amino groups and higher boiling temperatures from more rigid ionic crystallites in the complex ion ionomers leading to the enhanced modulus. Monoamines or polyamines with amino groups attached to flexible chains such as polyether and polysiloxane scarcely develop ionic crystallites and preferentially solvate the amorphous region including ionic groups leading to the decreased modulus. These results provide us with the fundamental information to control the modulus of ionomers.     

Fourier transform ir studies of the degradation of polyacrylonitrile copolymers—II: Acrylonitrile/methacrylic acid copolymers

The results of a Fourier transform IR study of the degradation of an acrylonitrile copolymer containing approx. 4 wt% of methacrylic acid, at 130°C under a reduced pressure of 5 × 10^?2 Torr, are presented. A mechanism is proposed for the degradation that is consistent with the IR spectral evidence. Additionally, we have determined from our experimental results that methacrylic acid is incorporated into the cyclized degraded structure and that, on average, three to four acrylonitrile acids are cyclized for each acid initiation.     

Dielectric studies of proton migration and relaxation in wet cellulose and its derivatives

Dielectric relaxation data are reported over a frequency range 400 Hz to 12 kHz and over a temperature range 193 to 323K on cellulose, cellulose acetate and ethyl cellulose with various water contents. A relaxation peak shifted to the low temperature side of the beta process was observed for cellulose acetate with less than 4% water. The effect of water addition in the case of cellulose and ethyl cellulose was initially to increase the amplitude of the loss associated with side group motion. Above 4% water content, the low temperature relaxation in cellulose acetate moves to lower temperatures and an increase in the loss is observed at high temperatures. Similar behaviour was observed in cellulose and ethyl cellulose. A transformation of the frequency dependent conductivity data allowed identification of a hopping conduction process at high temperature. The lowest temperature processes are analyzed in terms of dipole relaxation and the higher temperature features in terms of proton migration.     

Effect of vinylacetate content on crystallinity and second-order transitions in ethylene—vinylacetate copolymers

Thermal characteristics of ethylene—vinylacetate (EVA) copolymers having vinylacetate contents ranging from 5 to 40 w/w % are studied by differential scanning calorimetry. It is first shown that EVA copolymers having a vinylacetate content lower than 30 w/w % obey the Flory and Burfield theories of copolymer crystallisation. The minimum sequence length of CH₂ ethylenic entities required to participate in a crystalline lamella is also deduced. One can conclude that EVA copolymers represent cases of “total exclusion” of the noncrystallizable comonomer. Moreover, it is observed that when the vinylacetate content is increased, the relative quantity of polyethylene amorphous phase increases and the degree of crystallinity decreases; whereas the β transition temperature of a characteristic-oriented amorphous phase is kept constant. A phase model of ethylene-vinylacetate copolymers, based on an enrichment process of the interlamellar amorphous phase by polyethylene segments originating from the crystalline phase, at increasing vinylacetate content, is proposed. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 1903–1912, 1997     

Morphology and properties of nanocomposites formed from ethylene/methacrylic acid copolymers and organoclays

Nanocomposites were prepared by melt mixing ethylene/methacrylic acid copolymers and organoclays, which were compared to equivalent composites prepared from low-density polyethylene (LDPE) and a sodium ionomer of poly(ethylene-co-methacrylic acid). The effects of matrix modification and organoclay structure on the morphology and properties of these nanocomposites were evaluated using stress-strain analysis, wide-angle X-ray scattering (WAXS), and transmission electron microscopy coupled with particle analysis. With all four polymers, the use of a two-tailed organoclay, M₂(HT)₂, led to the formation of more exfoliated nanocomposites than a one-tailed organoclay, M₃(HT)₁. Nanocomposites prepared from ethylene/methacrylic acid copolymers revealed better exfoliation compared to similar composites prepared from LDPE. It seems that the presence of relatively small quantities (1.3-3.1 mol%) of the polar methacrylic acid monomer aids in improving the organoclay exfoliation efficiency of these polymers. Nanocomposites prepared from the sodium ionomer of poly(ethylene-co-methacrylic acid) exhibited the highest levels of organoclay exfoliation compared to all other polymers examined in this study. However, from the observations made in this study, it was not possible to determine conclusively the relative interaction of carboxyl acid groups versus the salt form with the organoclay and, thus, their influence on exfoliation; additional studies will be needed to reach a conclusion on this important point.     

Preparation of block copolymers of styrene and methacrylic acid

A range of block copolymers of styrene and methacrylic acid has been prepared by the suspension method involving migration of a growing radical across a phase boundary. The way in which copolymer composition varies with change in the amount of the two monomers in the reaction mixture has been studied, and explanations are suggested to account for these variations. Two methods, involving calculation from solubility data and thermogravimetric analysis respectively, have been used to give an estimate of the length and composition of the blocks.     

Dielectric relaxation of poly(chlorostyrenes) and their copolymers in the primary transition region

Dielectric relaxation measurements were carried out on a series of bulk poly(chlorostyrene) homopolymers and random copolymers over the frequency range from 50 to 100 kHz and at temperatures in the neighbourhood of the glass transitions of the polymers thus encompassing the α relaxation. Homopolymers examined were polystyrene (PS), poly(2-chlorostyrene) (P2CS), poly(3-chlorostyrene) (P3CS), and poly(4-chlorostyrene) (P4CS). Copolymers were poly(styrene-co-2-chlorostyrene) (PS2CS), poly(styrene-co-4-chlorostyrene) (PS4CS), and poly(2-chlorostyrene-co-4-chlorostyrene) (P2CS4CS). The dielectric data were analysed to yield dipole moments and Kirkwood—Fröhlich correlation parameters. The shapes of the dielectric loss curves were also taken into account. Glass transition temperatures were determined by differential scanning calorimetry (d.s.c.). It was concluded that the phenyl ring rotates freely in the α relaxation regions of PS, P4CS, and P3CS, but not in P2CS. The dipole moments of the copolymers are correlated with dyad distributions calculated from reactivity ratios.     

Segmented organosiloxane copolymers: 2 Thermal and mechanical properties of siloxane—urea copolymers

The structure-property behaviour of new siloxane-urea containing segmented copolymers has been investigated. Amino-propyl terminated poly(dimethylsiloxane) oligomers of from 900–3660 M_n were reacted with various diisocynates to form segmented copolymers with urea linkages. The length of the hard segments in these copolymers corresponds approximately to the length of the diisocynate unit employed. A number of mechanical and thermal properties were investigated for these phase separated materials. It was found that the performance of these copolymers was effected by varying the hard segment type and/or content and that high strength necessitates a microphase texture. The two phase nature of these copolymers was verified by dynamic mechanical, thermal and SAXS studies. The phase separation was found to occur in these copolymers even with 6% hard segment by weight. In conclusion, these materials displayed a behaviour similar to the segmented polyurethanes and were found to be superior to the unfilled silicone elastomers.