Influence of molecular weight on the dynamic mechanical properties of poly(methyl methacrylate)

Using a new parallel beam apparatus, the dynamic mechanical properties of poly-(methyl methacrylate) were determined over a wide range of molecular weights (1500< < <600 000). Results showed that the modulus (25 °C) was only slightly dependent on chain length, and equalled 2.3×10⁹ Pa for the highest molecular weight scanned. Simultaneous acquisition of- and-relaxations indicated a decrease inT in accordance with Gibbs' relation, whileT was invariant. BothT =111° andT =40° corroborated previous results from several sources, including dynamic mechanical measurements. Such modulus and glass transition data are essential to the calculation of fracture toughness and to the assessment of radiation damage of acrylic, respectively.

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Zusammenfassung Unter Anwendung eines neuen Parallelstrahlgerätes wurden die dynamischen mechanischen Eigenschaften von Poly(methylmethacrylat) in einem weiten Molmassenbereich (1500< <600 000) bestimmt. Die Ergebnisse zeigten, daß der Modul (25°) nur wenig von der Kettenlänge abhängig und für die höchste erfaßte Molmasse gleich 2.3× ×10⁹ Pa war. Die gleichwertige Erfassung der- und-Relaxationen zeigte in Übereinstimmung mit der Gibbs-schen Abhängigkeit eine Abnahme vonT währendT unverändert blieb. SowohlT =111° als auchT =40° bestätigten frühere Ergebnisse verschiedenen Ursprungs, dynamische mechanische Messungen mit inbegriffen. Solch ein Modul und Glas-Übergangsdaten sind zur Berechnung der Bruchfestigkeit bzw. zur Bestimmung der Bestrahlungsschäden in Acrylaten unerläßlich.

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Résumé En se servant d'un nouvel appareil à rayons parallèles, on a déterminé les propriétés mécaniques dynamiques du poly(méthyl-méthacrylate) dans un large intervalle de poids moléculaires (1500< <600 000). Les résultats on montré que le module (25°) ne dépend que peu de la longueur de la chaîne et est égal à 2.3×10⁹ Pa pour le plus haut poids moléculaire étudié. L'acquisition simultanée des relaxations et a indiqué, en accord avec la relation de Gibbs, une diminution deT tandis queT s'avere invariable. Les valeursT =111°et}T =40° ont corroboré toutes deux des résultats antérieurs de diverses sources, y compris des mesures mécanique dynamiques. Un tel module ainsi que les données de la transition vitreuse sont essentiels pour calculer la résistance à la rupture, et pour déterminer les dommages par irradiation des matières acryliques.

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, (1500 < < 600 000). , (25°) 2.3&#x0445;10⁹ . - - T , T . T =111° T =40° , . .

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This investigation was supported by NIH Research Grant No. DE 02668, RCDA number DE 00052 (R.P.K.), and RFA number DE 05132 (A.R.G.).     

Some physical and mechanical properties of isotactic-atactic poly(methyl methacrylate) blends and stereoblocks

Dynamic-mechanical, DSC, and fracture-toughness measurements are reported for blends of it-PMMA with at-PMMA and syndiotactic-rich PMMA, both in the amorphous state and after solvent and thermally induced crystallization. Crystalline stereocomplex forms even in the blends of 74% isolactic with commercial at-PMMA under SIC. Some stereoblock PMMA shows two melting points and two distinct crystalline forms; one corresponds to it-PMMA the other probably to stereocomplex. Microcrystallinity in the blends greatly enhances stiffness. The decline of the storage shear modulus with temperature involves several processes. Blending of it-PMMA (even low mol. wt) into at-PMMA greatly improves its fracture toughness.     

Physical aspects of the effect of chain transfer agents on the properties of poly(methyl methacrylate)

It was found that PMMA prepared in the presence of the chain transfer agents dodecyl mercaptan and pentamethyldisilane possess noticeably better properties as a radiation resist relative to the polymer with a close molecular mass obtained in the absence of a transfer agent. By means of densitometry, GPC, calorimetry, small-angle X-ray scattering, and light scattering, it was shown that the existence of weak bonds, the narrowing of the molecular-mass distribution, and the formation of a looser supermolecular structure are responsible for the enhanced radiation sensitivity of the polymers prepared under the chain-transfer reaction conditions.     

Flow properties of poly(methyl methacrylate) solutions

Viscosity and normal stress behavior were measured for poly(methyl methacrylate) samples of various average molecular weights in diethyl phthalate solution at 30 and 60°C. All samples conformed approximately to the most probable distriution (M?_w/M?_n = 2). Concentrations ranged from 0.113 to 0.38 g/ml, and M?_w from 53,800 to 1,620,000. Despite considerable evidence in the literature of unusual linear viscoelastic behavior for this polymer, its nonlinear properties appear to be rather conventional. The viscosity–shear rate master curve was similar to that found earlier for concentrated solutions of polystyrene and poly(vinyl acetate) of comparable molecular-weight distribution. The viscosity time constant τ_o parallels τ_R, the characteristic time of the Rouse model, although the residual dependence of τ_o/τ_R on concentration and molecular weight appears to be slightly different from that for polystyrene and poly(vinyl acetate). Similar conclusions apply to the recoverable compliance J_e,^o estimated from the normal stress behavior of each solution, and its relationship to the Rouse model compliance J_R.     

Studies on the influence of physical aging processes on electret properties of amorphous poly(methyl methacrylate)

The influence of physical aging processes on the electret properties of amorphous poly(methyl methacrylate) was investigated. The experimental method of choice was the thermally stimulated discharge (TSD) technique. The result of these studies is that aging influences the magnitude of the electrical polarization within the glassy state and the thermal stability of the polarization originating from the frozen-in dipole orientation and from trapped charges. The effects of aging on electret properties can, to a good approximation, be accounted for on the basis of the phenomenological aging theory, as proposed by Kovacs et al. More detailed information on the relation between relaxation properties and aging of electret properties can be obtained from an analysis of the experimental results, based on the universal law approach, as proposed by Ngai et al.     

Solvent effect on NMR spectra of poly(methyl methacrylate)

The NMR spectra of stereoblock poly(methyl methacrylate) in several solvents were measured. It is concluded from the following experimental results that the solute–solvent complexes are formed in benzene solution: the chemical shifts measured in C₆H₆ go to a lower field than do those in CDCl₃, except those of the ester methyl group, which splits into three resonances, and the shifts in the aromatic solvents are so different from those in the aliphatic solvents that Buckingham's theory cannot be applied to the results. The analysis of the temperature dependence of the chemical shifts of PMMA in benzene solution gave the heat of formation of the complex: ΔH = 2.8 ± 0.5 kcal./mole.     

A calorimetric investigation of the formation of a stereocomplex in poly(methyl methacrylate) solutions

The heat of formation ΔH of the stereocomplex of iso + syndiotactic poly(methyl methacrylate) in a 1 per cent solution in dimethylformamide and in toluene was measured. From the concentration dependence of ΔH it may be inferred that multimolecular aggregates are formed, with a composition given by the ratio syn: iso = 1·5: 1 to 2: 1. The measurements also indicate a strong dependence of the thermal effect on the quality of the solvent and on the tacticity of both polymer components.     

Structures and thermal properties of chitosan-modified poly(methyl methacrylate)

The emulsion polymerization of methyl methacrylate in the presence of chitosan with potassium persulfate (KPS) as an initiator was examined in a previous article. The free radicals that dissociated from KPS not only initiated the polymerization but also degraded the chitosan molecules. Therefore, in addition to its role as a cationic surfactant, chitosan also participated in the polymerization reaction. When the polymerization was complete, the latex polymer consisted of poly(methyl methacrylate) (PMMA) homopolymer and chitosan–PMMA copolymer. In this article, the structures and thermal properties of latex polymers are examined. Gel permeation chromatography was used to measure the molecular weight of the PMMA homopolymer, with the copolymer composition determined by an elemental analyzer. Scanning and transmission electronic microscopes were used to measure the size of latex particles from different reaction systems. The surface charges of latex particles at several different pH values were determined by the measurement of the ζ potential. All results agreed with the reaction mechanism proposed in the previous article. Finally, the presence of rigid chitosan increased the glass-transition temperature of the final latex polymers. Thermogravimetric analysis showed that the degradation behavior of latex polymers was similar to the unzipping mechanism of PMMA, yet the presence of chitosan units hindered the unzipping of the main chains in chitosan–PMMA copolymers. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1646–1655, 2001     

Effect of tacticity on permeation properties of poly(methyl methacrylate)

The effect of stereoregularity on gas permeation properties of poly(methyl methacrylate) (PMMA) was investigated. The gas permeability coefficients for He, H₂, O₂, N₂, Ar, CH₄, and CO₂ at 35°C near atmospheric pressure have been measured for three different PMMAs. Apparent diffusion and solubility coefficients were obtained from time lag data, and these were compared with data for a commercial PMMA previously reported. The permeability, solubility, and diffusion coefficients increase as the content of syndiotactic sequences increases. These observations are consistent with more dense packing of the isotactic form in the glassy state that stems in part from its lower glass transition temperature. The transport behavior for a 50:50 isotactic/syndiotactic blend was also studied. These so-called stereocomplexes exhibit permeation behavior comparable to other weakly interacting miscible blend systems.     

Dynamics of adsorbed poly(methyl acrylate) and poly(methyl methacrylate) on silica

Deuterium NMR and modulated differential scanning calorimetry (MDSC) were used to probe the behavior of ultrathin adsorbed poly(methyl acrylate) (PMA). The spectra for the bulk methyl-labeled PMA-d₃ were consistent with the motions of the polymer segments being spatially homogeneous. For the polymers adsorbed on silica, multicomponent line shapes were observed. The segmental mobility of the surface polymers increased with increased adsorbed amounts. In contrast to the behavior of the polymers in bulk, the adsorbed lower-molecular-mass PMA-d₃ was less mobile than the adsorbed high-molecular-mass polymer. The presence of a polymer overlayer was sufficient to suppress the enhanced mobility of the more-mobile segments of the adsorbed (inner) polymer. MDSC studies on adsorbed poly(methyl methacrylate) showed that the glass-transition temperature of the thin polymer films increased and broadened compared to the behavior of the polymer in bulk. The presence of a motional gradient with the less-mobile segments near the solid-polymer interface and the more-mobile segments near the polymer-air interface was consistent with the experimental observations.     

Mechanical properties of methanol crazes in poly(methyl methacrylate)

Methanol crazes are grown from sharp cracks in poly(methyl methacrylate) (PMMA). The craze thickness profile is measured using a replica technique after the craze opening displacement profile of the growing craze has been measured with holographic interferometry. The craze strain profile is then computed from these data. The craze surface stress profile is determined by two methods: (1) from the uniaxial strain profile of regions adjacent to the craze as measured from the fringe spacing on the reconstructed hologram and (2) from the craze opening displacement profile using the Fourier transform method of Sneddon. From the surface stress and craze-strain profiles a true stress-strain curve for the craze fibrils has been constructed. The extrapolated fibril yield stress is in good agreement with the yield stress of bulk PMMA plasticized with methanol indicating that surface tension effects do not contribute importantly to craze fibril mechanical properties at room temperature. The craze strain increases from 0.4 near the craze tip to 1.4 near the craze base implying that methanol crazes in PMMA thicken by further straining of the existing craze fibrils and not by drawing new material into the craze from the craze surfaces. The primordial craze thickness, i.e., the original thickness of polymer which fibrillates to form the craze fibrils, is approximately 1 μm and is constant over most of the craze length. This thickness may be determined by diffusion of methanol normal to the craze surfaces in a process zone just behind the craze tip.     

Photodegradation of poly(methyl methacrylate)

The vacuum photodegradation at 30°C. of poly(methyl methacrylate) and copolymers with acrylaldehyde, methacrylaldehyde, and methyl acrylate has been studied. The polymers were examined in the form of expanded films as produced by a freeze-drying technique. At least one molecule of carbon monoxide is evolved for each chain scission. It is concluded that chain scission in poly(methyl methacrylate) is primarily the result of photoinduced aldehyde groups.     

Dynamic mechanical and thermal properties of physically compatibilized natural rubber/poly(methyl methacrylate) blends by the addition of natural rubber‐graft‐ poly(methyl methacrylate)

The dynamic mechanical and thermal properties of natural rubber/poly (methyl methacrylate) blends (NR/PMMA) with and without the addition of graft copolymer (NR‐g‐PMMA) have been investigated. Dynamic mechanical spectroscopy is used to examine the effect of compatibilizer loading on storage modulus (E′), loss modulus (E″) and loss tangent (tan δ) at different temperatures and at different frequencies. The morphology of the blends indicates that the size of the dispersed phase decreased by the addition of a few percent of the graft copolymer followed by a leveling off at higher concentrations. This is an indication of interfacial saturation. Attempts have been made to correlate morphology with dynamic mechanical properties. Various models have been used to fit the experimental viscoelastic results. Differential scanning calorimetry has been used to analyze the glass‐transition temperatures of the blends. The thermal stability of the blends has been analyzed by thermogravimetry. Compatibilized blends are found to be more thermally stable than uncompatibilized blends. Finally the miscibility and mechanical properties of the blends annealed above T_g are evaluated. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 525–536, 2000     

Energetics of low-molecular-mass products of mechanical fracture of poly(methyl methacrylate)

It is experimentally revealed that monomer and water molecules released during the fracture of PMMA have a bimodal velocity distribution. The first distribution peak for the monomer corresponds to energetic (hot) MMA molecules (0.13–0.70 eV), and the second peak is attributed to MMA molecules bearing a low energy (0.016–0.060 eV). On the basis of the results of earlier theoretical studies of the mechanically induced polymer-chain scission, it was concluded that the energetic monomer molecules are produced immediately in the event of mechanical chain rupture and are nonthermal in nature. In the bimodal velocity distribution of occluded water molecules desorbed from a subsonic crack, the first and the second peaks are attributed to “hot” and “cold” molecules with translational temperatures of 605 ± 180 K and 53 ± 5 K, respectively. A possible mechanism of the mechanically induced desorption of occluded water is discussed. The mechanodesorption of water molecules is due to the portion of vibrational energy transferred to side methyl carboxylate groups that retain water molecules by the unloading-wave front traveling along the main chain from a macromolecule scission site. Along with hot water molecules, a considerable amount of hot free hydroxyls were detected. The mechanism of formation of the latter species is associated with the double-well structure of the hydrogen bond potential and similar to the mechanism of mechanodesorption of hot molecules of water.     

An analysis of the crystallization behavior of poly(ethylene oxide)/poly(methyl methacrylate) blends by spectroscopic and calorimetric techniques

Infrared spectra in conjunction with calorimetric measurements have been used to follow the crystallization process and microstructural changes of poly(ethylene oxide) (PEO) in poly(ethylene oxide) and poly(methyl methacrylate) (PMMA) blends. We have given particular attention to compositions containing low PEO concentrations. The crystallization behavior and the resultant microstructures of PEO are strongly perturbed by the presence of PMMA. In addition, we found phase separation and trans sequences of PEO to be present, especially at low PEO concentrations.     

Study of the influence of physical aging on macroradical decay in poly(methyl methacrylate)

The macroradical decay in poly(methyl methacrylate) samples with different thermal histories was investigated in the temperature interval 20–100 °C using ESR spectroscopy and the second order kinetic model. The rate constants exhibit two different regimes with the transitions atT _tr=68±1°C which are independent of thermal treatment. ForT<T _tr andT>T _tr the rate constants as well as the corresponding activation parameters are sensitive to history because of different physical microstructures. The compensation law, i.e., the linear relation between lnk _{o, eff} andE _eff, was analyzed in terms of the so-called compensation quantitiesk _c andT _c and a proximity betweenT _c=T _tr andT _o=53±3 °C — Vogel temperature for -segmental dynamics was found. A comparison of kinetic and dynamic data suggests that the decay of terminal macroradicals in the low-temperature region is controlled by secondary relaxations and that the -mobility contributes to a more rapid decay at higher temperatures belowT _g.     

Stabilizing effect of oxygen on thermal degradation of poly(methyl methacrylate)

The thermal degradation of poly(methyl methacrylate) has been studied under nitrogen and air. The presence of oxygen increases the initial decomposition temperature by 70°C. The stabilizing effect of oxygen is explained by the formation of thermally stable radical species that suppress unzipping of the polymer. This assumption is supported by the experimental fact that introduction of NO into the gaseous atmosphere increases the initial decomposition temperature by more than 100°C.     

Improvements of properties of asphalt by poly(methyl methacrylate) additives

This article presents the effect of adding poly(methyl methacrylate) (PMMA) with different molecular weights on the mechanical properties of asphalt in terms of durability, strength, and resistance to rutting. By controlling the time of reaction we obtained PMMA of two different molecular weights: PMMA1 and PMMA2. The ageing properties of polymer modified asphalts were studied using the thin film over (oven) a test. A hot storage stability test was carried out for polymer modified binder. The physical properties of asphalt modified with PMMA including penetration value and softening point were examined at two different temperatures. Resilient modulus test was evaluated by a Universal Testing Machine. Results showed that an incorporation of PMMA into asphalt binder has significantly improved its properties under studies. Indirect tensile strength test and durability performance of the modified asphalts was evaluated as well. The resulted modification was found to be dependent on the polymer molecular weight. The PMMA1 exhibited effective and cheerful results.     

Synthesis and thermal properties of poly(methyl methacrylate)-graft-(cellobiosylamine-C15)

Model experiments for synthesis of a comb-shaped copolymer with cellulose side-chains were performed with cellobiose derivatives. A novel cellobiose monomer, N-(15-methacryloyloxypentadecanoyl)-2,3,6-tri-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-β-d-glucopyranosyl)-β-d-glucopyranosylamine (2) was prepared from heptaacetylcellobiosyl- amine. Homopolymerization of cellobiose monomer 2 and copolymerization of monomer 2 with methyl methacrylate (MMA) were performed using 2,2′-azobis(isobutyronitrile) (AIBN) as an initiator to obtain homopolymers 3-i (i = 1–4) and copolymers 3-i (i = 5–7), poly(methyl methacrylate)-graft-(heptaacetylcellobiosylamine-C15). The size exclusion chromatography—multi-angle laser light scattering (SEC-MALS) measurements revealed that comb-shaped homopolymers 3-i (i = 1–4) had more compact structures compared to copolymers 3-i (i = 5–7) at the same elution volume. Selective deacetylation of polymers 3-i (i = 1–7) gave novel cellobiose polymers 4-i (i = 1–7), poly(methyl methacrylate)-graft-(cellobiosylamine-C15). The amide linkages between cellobiose moiety and long-chain alkyl group, and the ester linkages between PMMA main-chain and long-chain alkyl group remained after deprotection. The differential scanning calorimetry (DSC) measurements revealed that the T _gs of the polymers 4-i (i = 1, 5, 6, 7) increased with increasing cellobiose composition in the polymers. It was indicated that cellobiose moieties of polymers 4-i (i = 1, 5, 6, 7) reduced the mobility of PMMA main-chain.