The transport of methyl methacrylate monomer in poly(methyl methacrylate)

The absorption kinetics and equlibria of methyl methacrylate monomer into poly(methyl methacrylate) were studied over a range of penetrant activities. The interval sorption kinetics at elevated activities were determined, compared, and contrasted with the integral sorption experiments in previously unpenetrated film samples. The sorption kinetics in previously unpenetrated films were predominantly case II or relaxation controlled at high activities. A Fickian contribution to the overall kinetics was apparent at lower activities. In contrast, interval sorption, at elevated activities in previously equilibrated and plasticized samples, followed Fickian kinetics rather closely, whereas resorption, over an activity range which involved a traversal of the effective T_g, was characterized by more complicated kinetics involving a super case II mechanism at long times. These composite results reinforce the notion that the kinetics describing penetration of a single penetrant into a single polymer are extremely sensitive to the boundary condition imposed upon the polymeric sorbent.     

Miscibility of poly(methoxymethyl methacrylate) and poly(methylthiomethyl methacrylate) with poly(methyl methacrylate)

Summary Poly(n-propyl methacrylate) is known to be immiscible with poly(methyl methacrylate) (PMMA). However, we have found that poly(methoxymethyl methacrylate) is miscible with PMMA, indicating the importance of ether oxygen atoms in achieving miscibility. On the other hand, poly(methylthiomethyl methacrylate) is immiscible with PMMA.     

Stereocomplex formation in polybutadiene-syndiotactic poly(methyl methacrylate) block copolymers blended with isotactic poly(methyl methacrylate)

Summary The process of stereocomplexation in blends of isotactic poly(methyl methacrylate)s and polybutadiene-syndiotactic poly(methyl methacrylate) diblock copolymers was studied by differential scanning calorimetry as a function of molar mass of the constituents, annealing time and temperature. The amount of complex formed is dependent on these three parameters, while the temperature of decomposition of the complex is only dependent on the annealing temperature. Complex formation can be observed in blends containing a copolymer with a very low molar mass syndiotactic poly(methyl methacrylate) block (Mn=700). In contrast to homopolymer blends, for which two endotherms of decomposition were generally reported, only one endotherm is observed for copolymer-homopolymer blends. This behavior is attributed to the elastomer block.     

Thermo-oxidative stability of poly(methyl methacrylate)/poly(methyl methacrylate)-grafted SiO2 nanocomposites

Thermo-oxidative stability of PMMA-grafted SiO₂ and PMMA/PMMA-grafted SiO₂ nanocomposites was investigated by conventional non-isothermal gravimetric technique. It was interesting to find that PMMA-grafted SiO₂ nanoparticles exhibited higher thermo-oxidative stability than that of PMMA. The apparent activation energy of PMMA-grafted SiO₂ nanoparticles increased with the grafting ratio of PMMA from SiO₂, which was estimated by Kissinger method. This indicates that the strong interactions existing between the grafted chains are responsible for the enhanced thermo-oxidative stability of PMMA-grafted SiO₂ nanoparticles. However, the grafting ratio of PMMA from SiO₂ in nanoparticles has only limited effect on the thermo-oxidative stability of PMMA/PMMA-grafted SiO₂ nanocomposites due to a much lower content of grafted PMMA in the nanoparticles relative to PMMA. The increased thermo-oxidative stability of PMMA/PMMA-grafted SiO₂ nanocomposites is possibly resulted from the increased SiO₂ content in the nanocomposites, in which the grafting ratio of PMMA in PMMA-grafted SiO₂ nanoparticles is kept almost as a constant. The glass transition temperature (T _g) of PMMA/PMMA-grafted SiO₂ nanocomposites is about 25 °C and is higher than that of PMMA. The grafting ratio of PMMA from SiO₂ in the nanoparticles has no qualitative effects on the T _g of the nanocomposites.     

Conformational transition in poly(methyl methacrylate)

Summary This paper refers to a systematic and comparative study of the intrinsic viscosities of fractions of atactic and syndiotactic samples of PMMA in various polar solvents as a function of temperature. The data allow determination of important changes in the conformation of the polymer.     

Linear and non-linear viscoelastic behavior of poly(methyl methacrylate) in the hard region

The relaxation behavior of poly(methyl methacrylate) in the hard region is caused by hindered rotations of the methoxycarbonyl side groups of the molecules. Measurements of the Young's modulus and the shear modulus at different frequencies, temperatures and strains lead to the following conclusions: each moving side group is surrounded by the elastic matrix of mean chains, The elasticity of this matrix depends on volume and temperature. Also the activation energy of the moving side group depends on volume and temperature, because the activation energy is the sum of an intramolecular and an intermolecular component. Due to the statistical entanglement of the molecules, the intermolecular contribution to the activation energy has a statistical distribution depending on volume. The reaction rate theory is of value for interpreting the viscoelastic behavior in the linear and non-linear range if several considerations are followed.     

Photodegradation kinetics of methyl salicylate in poly(methyl methacrylate)

It has been found that methyl salicylate (MS) undergoes a photoinduced decarboxylation to form phenol with a quantum yield of ca. 8 × 10^?5. The reaction is first order and the rate constant is proportional to the irradiance used. An activation energy of 1.2 kcal/mol was determined. Computer simulations were used to predict whether sufficient UV screening would be provided by MS-containing PMMA lenses over the projected lifetime of solar photovoltaic devices. An effective screening lifetime of less than 2 years is predicted.     

The limits of linear viscoelasticity in poly(methyl methacrylate) and poly(ethyl methacrylate)

The limit of linear viscoelasticity is determined for poly(methyl methacrylate) (PMMA) and poly(ethyl methacrylate) (PEMA) in uniaxial tension creep over the temperature range of 20° to T_g ?10°C. The time span covered is from 10 to 1000 sec. The linear limit is defined as the point at which the creep compliance deviates by more than 1% from its mean value in the linear viscoelastic range. For both materials, the stress limit of linear viscoelasticity falls to a minimum or plateau level at a temperature below T_g. It is suggested that the β-mechanism plays an important role in the existence of this minimum.     

Thermal stability of poly(methyl methacrylate)

Summary The average solid-state molecular structures of end-groups generated through chain termination reactions in the polymerization of methyl methacrylate have been derived from published crystallographic data. Evidence is provided for the reduced stability of the head-head chain-termination configuration and in support of the postulate that it is a preferred site of chain scission. Comparable evidence for the unsaturated end group has not been found.     

Impact failure of poly(methyl methacrylate)

Damage development during instrumented falling weight impact (IFWIM) testing of poly(methyl methacrylate) (PMMA) is recorded using short pulse photography. The first visible damage is cracking on application of the peak force. Finite element analysis predicts the deformation and state of stress throughout the specimen until the first point of failure is reached. A variation in the specimen geometry produces a significant change in initial failure energy, while the maximum tensile stress is approximately constant. The proposed failure criterion is the attainment of a critical time-dependent value of tensile stress. © 1992 John Wiley & Sons, Inc.     

Transport of methanol in poly(methyl methacrylate)

The transport kinetics of liquid methanol in PMMA sheet (Perspex) have been studied over the temperature range 23° to 63°C. At the lower temperatures the transport is typical Case II; the methanol penetrating the polymer behind a sharp front which moves at constant velocity. For higher temperatures the concentration of methanol at the front and the front velocity both decrease with increasing penetration. These factors, which are no doubt related, combine to give mass absorption kinetics in which the exponent of time is no longer unity (Case II) but approaches 0.5, the value typical of Fickian diffusion. Iodine has been added to the methanol to make the positions of the penetration fronts readily visible. The iodine does not affect either the rate of penetration or the equilibrium absorption. Measurements of colour density profiles on thin cross-sections using a microdensitometer give a reliable indication of the true methanol profile. The rate at which the methanol penetrates the glassy polymer is proportional to its concentration at the advancing fronts. The apparent activation energy for methanol penetration for constant concentration at the fronts is 25 kcal/mol.     

Time-dependent failure of poly(methyl methacrylate)

A theory has been developed to explain the time-dependent failure of poly(methyl methacrylate) (PMMA) (and possibly all glassy polymers). The analysis uses the concepts of linear elastic fracture mechanics and it has been shown that by making simple assumptions it is possible to predict the lifetimes of PMMA specimens under static load from the strain-rate dependence of Young's modulus for the material.     

Comparison of the phase behaviour of the liquid-crystalline polymer/poly(methyl methacrylate) and poly(vinyl acetate)/poly(methyl methacrylate) blends

The phase behaviour of blends of a liquid-crystalline polymer (LCP) and poly(methyl methacrylate) (PMMA), as well as the phase state of blends of PMMA and poly(vinyl acetate) (PVA) has been investigated using light scattering and phase-contrast optical microscopy. The blends of LCP and PMMA have been obtained by coagulation from ternary solutions. The cloud point curves were determined. It was established that both pairs demix upon heating, ie have an LCST. In the region of intermediate composition, the phase separation proceeds according to a spinodal mechanism; however for LCP/PMMA blends, the decomposition proceeds according to a non-linear regime from the very onset. In the region of small amounts of LCP, the phase separation follows a mechanism of nucleation and growth. For PMMA/PVA blends, the spinodal decomposition proceeds according to a linear regime, in spite of the molecular mobility that PVA chains develop at lower temperatures. Only after prolonged heat treatment does the process transit to a non-linear regime. The data show a similarity between the phase behaviour of blends of liquid-crystalline and of flexible amorphous polymers. The distinction consists of the absence of a linear regime of decomposition for LCP-PMMA blends. © 1999 Society of Chemical Industry     

Optical waveguiding in doped poly(methyl methacrylate)

Poly(methyl methacrylate) doped with the photoinitiators benzil and benzildimethylketal is dissolved in the monomer MMA. From the solutions, planar waveguides and optically-recorded strip waveguides are fabricated on quartz substrates. Mode spectra and total losses are investigated and indicate a minimum loss value of about 0.015 dB mm^?1 for photoinitiator concentrations of about 10%. The results also point to a considerable influence of surface irregularities.     

Temperature-dependent interaction parameters of poly(methyl methacrylate)/poly(2-vinyl pyridine) and poly(methyl methacrylate)/poly(4-vinyl pyridine) pairs

Temperature-dependent interaction parameters (α) of poly(methyl methacrylate)/poly(2-vinyl pyridine) (PMMA/P2VP) pair and PMMA/poly(4-vinyl pyridine) (PMMA/P4VP) pair were obtained from the SAXS profiles at various temperatures, and curve fitting to the random phase approximation theory. For this purpose, symmetric P2VP-block-PMMA and P4VP-block-PMMA copolymers were synthesized anionically. The molecular weights of both block copolymers were controlled to exhibit the disordered state over the entire experimental temperatures. We found that the value of α for PMMA/P4VP was larger than PMMA/P2VP, similar to polystyrene (PS)/poly(vinyl pyridine) pairs. However, the difference between in α between PMMA/P2VP and PMMA/P4VP was much smaller than that between PS/P2VP and PS/P4VP. This might be attributed to the hydrophilic PMMA block compared with hydrophobic PS block. Finally, the order-to-disorder transition temperature for symmetric P2VP-block-PMMA copolymers was determined by small angle X-ray scattering and birefringence methods.     

Study of sintering of poly(methyl methacrylate)

Sintering of poly(methyl metacrylate) spheres to the blocks of the same material was studied at temperatures ranging from 127° to 207°C. The analysis of the data based on the empirical Ostwald relation indicates that the predominant mechanism responsible for this process is non-Newtonian viscous flow. The type of the flow changes with temperature of sintering, being pseudo-plastic at lower temperatures and tending to dilatancy at higher ones.     

Modified frontal polymerization of poly(methyl methacrylate)

In this work, we propose a modified frontal polymerization method to build a uniform reaction front by gradually immersing the reacting mixture in a thermal bath. This scheme allows uniform materials to be obtained with nearly constant molecular weights and polydispersities and a low residual monomer concentration. A comparative study of the molecular weight distributions of poly(methyl methacrylate)s obtained by bulk polymerization, frontal polymerization, and frontal polymerization with the proposed gradual immersion is presented. Samples obtained by these methods show that materials obtained by bulk polymerization and by frontal polymerization are less uniform than those obtained by frontal polymerization with gradual immersion in a thermal bath. The obtained uniformity is directly related to a stabilizing effect of the reaction front by the gradual immersion of the reactor in a constant‐temperature bath and to a reduction in the reaction rate promoted by a moderate transfer agent concentration. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Nonlinear mechanical spectrometry of poly(methyl methacrylate)

Data on the damping spectra of commercial poly(methyl methacrylate) (PMMA) are reported, both at low (of the order of 1 Hz) and at intermediate (of the order of 50 Hz) frequencies. It is shown that the damping does not only depend strongly on temperature and frequencies. It is shown that the damping does not only depend strongly on temperature and frequency but also on the strain amplitude applied to the specimen. In other words, the dynamic mechanical behavior of PMMA is nonlinear and cannot be described in terms of linear viscoelasticity. Finally, some aging effects in the damping, measured at low frequencies, are also reported. © 1995 John Wiley & Sons, Inc.