Methyl Methacrylate Oligomerically-Modified Clay and its Poly (Methyl Methacrylate) Nanocomposites

A methyl methacrylate oligomerically-modified clay was used to prepare poly(methyl methacrylate) clay nanocomposites by melt blending and the effect of the clay loading level on the modified clay and corresponding nanocomposite was studied. These nanocomposites were characterized by X-ray diffraction, transmission electron microscopy, thermogravimetric analysis and cone calorimetry. The results show a mixed intercalated/delaminated morphology with good nanodispersion. The compatibility between the methylacrylate-subsituted clay and poly(methyl methacrylate) (PMMA) are greatly improved compared to other oligomerically-modified clays

A Strategy for the Design of Flame Retardants: Cross-linking Processes

Cross-linking is identified as an effective means for flame retardation of polymers and schemes for the cross-linking of poly(ethylene terephthalate) and poly(methyl methacrylate) are presented. For poly(ethylene terephthalate) the scheme involves polymerization of the initially produced vinyl ester. This is followed by chain-stripping, producing a polyene, and cyclization of this polyene. For poly(methyl methacrylate) the scheme entails the formation of anhydride linkages between adjacent polymer strands. Evidence is presented to show the efficacy of these processes and information is produced to aid in the identification of new flame retardants

ABA triblock copolymers: from controlled synthesis to controlled function

The ABA amphiphilic block copolymers, poly(hydroxyethyl methacrylate-hlock-methylphenylsilane-block-hydroxyethyl methacrylate) (PHEMA-PMPS-PHEMA) and poly[oligo(ethylene glycol) methyl ether methacrylate-block-methylphenylsilane-block-oligo(ethylene glycol). methyl ether methacrylate] (POEGMA-PMPS-POEGMA) were successfully synthesised via atom transfer radical polymerisation (ATRP). Macroinitiators suitable for the ATRP of oligo(ethylene glycol) methyl ether methacrylate and 2-hydroxyethyl methacrylate were synthesised from the condensation reaction of alpha,omega-dihalopolymethylphenylsilane and 2'-hydroxyethyl 2-bromo-2-methylpropanoate. The copolymers were characterised using H-1 NMR and C-13 NMR spectroscopy and molecular weight characteristics were determined using size exclusion chromatography and H-1 NMR. The aggregation behaviour of some of the copolymers in water was studied using transmission and scanning electron microscopy and dynamic light scattering. These revealed the prevalent aggregate species to be micelles. Larger aggregates of 300-1000 nm diameter were also observed. The UV induced degradation of the aggregates was studied by UV-Vis spectroscopy. The thermal behaviour of selected copolymers was studied by differential scanning calorimetry and microphase separation of the two components was demonstrated

TGA/FTIR: An Extremely Useful Technique for Studying Polymer Degradation

Thermogravimetric analysis coupled to Fourier transform infrared spectroscopy, TGA/FTIR, has been used to probe the degradation of several polymeric systems. These include poly(methyl methacrylate) in the presence of various additives, graft copolymers of acrylonitrile-butadiene-styrene and styrene-butadiene with sodium methacrylate and styrene with acrylonitrile, blends of styrene-butadiene block copolymers with poly(vinylphosphonic acid) and poly(vinylsulfonic acid), and cross-linked polystyrenes. Additives may interact with poly(methyl methacrylate) by coordination to the carbonyl oxygen to a Lewis acid and the subsequent transfer of an electron from the polymer chain to the metal atom or by the formation of a radical which can trap the degrading radicals before they can undergo further degradation. When an inorganic char-former is graft copolymerized onto a polymer, there is a good correlation between TGA behavior in an inert atmosphere and thermal stability in air, but this is not true when the char is largely carbonific

Understanding the role of MAM molecular weight in the production of PMMA/MAM nanocellular polymers

Nanostructured polymer blends with CO2-philic domains can be used to produce nanocellular materials with controlled nucleation. It is well known that this nanostructuration can be induced by the addition of a block copolymer poly(methyl methacrylate)-poly(butyl acrylate)-poly(methyl methacrylate) (MAM) to a poly(methyl methacrylate) (PMMA) matrix. However, the effect of the block copolymer molecular weight on the production of nanocellular materials is still unknown. In this work, this effect is analysed by using three types of MAM triblock copolymers with different molecular weights, and a fixed blend ratio of 90 wt% PMMA and 10 wt% of MAM. Blends were produced by extrusion. As a result of the extrusion process, a non-equilibrium nanostructuration takes place in the blends, and the micelle density increases as MAM molecular weight increases. Micelle formation is proposed to occur as result of two mechanisms: dispersion, controlled by the extrusion parameters and the relative viscosities of the polymers, and self-assembly of MAM molecules in the dispersed domains. On the other hand, in the nanocellular materials produced with these blends, cell size decreases from 200 to 120 nm as MAM molecular weight increases. Cell growth is suggested to be controlled by the intermicelle distance and limited by the cell wall thickness. Furthermore, a theoretical explanation of the mechanisms underlying the limited expansion of PMMA/MAM systems is proposed and discussed

Low-density PMMA/MAM nanocellular polymers using low MAM contents: Production and characterization

Low-density nanocellular polymers are required to take advantage of the full potential of these materials as high efficient thermal insulators. However, their production is still a challenging task. One promising approach is the use of nanostructured polymer blends of poly(methyl methacrylate) (PMMA) and a block copolymer poly(methyl methacrylate)-poly(butyl acrylate)-poly(methyl methacrylate) (MAM), which are useful for promoting nucleation but seem to present a severe drawback, as apparently avoid low relative densities. In this work, new strategies to overcome this limitation and produce low-density nanocellular materials based on these blends are investigated. First, the effect of very low amounts of the MAM copolymer is analysed. It is detected that nanostructuration can be prevented using low copolymer contents, but nucleation is still enhanced as a result of the copolymer molecules with high CO2 affinity dispersed in the matrix, so nanocellular polymers are obtained using very low percentages of the copolymer. Second, the influence of the foaming temperature is studied. Results show that for systems in which there is not a clear nanostructuration, cells can grow more freely and smaller relative densities can be achieved. For these studies, blends of PMMA with MAM with copolymer contents from 10 wt% and as low as 0.1 wt% are used. For the first time, the production strategies proposed in this work have allowed obtaining low density (relative density 0.23) nanocellular polymers based on PMMA/MAM blends. Graphical abstrac

Electrostatic charging of non-polar colloids by reverse micelles

Colloids dispersed in a non-polar solvent become charged when reverse micelles are added. We study the charge of individual sterically-stabilized poly(methyl methacrylate) spheres dispersed in micellar solutions of the surfactants sodium bis(2-ethyl 1-hexyl) sulfosuccinate [AOT], zirconyl 2-ethyl hexanoate [Zr(Oct)$_{2}$], and a copolymer of poly(12-hydroxystearic acid)--poly(methyl methacrylate) [PHSA-PMMA]. Although the sign of the particle charge is positive for Zr(Oct)$_{2}$, negative for AOT, and essentially neutral for PHSA-PMMA the different micellar systems display a number of common features. In particular, we demonstrate that, over a wide range of concentrations, the colloid charge is independent of the number of micelles added and scales linearly with the colloid size. A simple thermodynamic model, in which the particle charge is generated by the competitive adsorption of both positive and negative micelles, is in good agreement with the experimental data

Graft co-polymerization of vinyl ers onto collagen. Part III. Characterization co-polymers and the mechanism of Copolymerization

Molecular weight and grafting sites of the poly (methyl methacrylate) side chains isolated from collagen-g-poly (methyl methacrylate) samples by acid hydrolysis are determined. Molecular weight of the polymers were in the order of 103. The number of grafting sites did not show any significant change with the time of exposure

Does organic modification of layered double hydroxides improve the fire performance of PMMA?

The effect of modified layered double hydroxides (LDHs) on fire properties of poly(methyl methacrylate) is investigated. Organically-modified LDHs were prepared via rehydration of calcined hydrotalcite in a palmitate solution. Composites consisting of the organo-LDHs, unmodified hydrotalcite and calcined oxides were prepared with poly(methyl methacrylate) using melt blending. Thermal and fire properties of the (nano)composites were studied. The thermogravimetric analyses of the composites show an increase in thermal stability. Fire performance, evaluated using cone calorimetry, show that organically-modified LDHs composites give the best reductions in peak heat release rate, PHRR, i.e., 51% at 10% weight loading. Dispersion of the LDHs was characterized using transmission electron microscopy and X–ray diffraction. Nanocomposite formation was observed with organically-modified LDHs, while the unmodified LDH composites gave only microcomposites

Mechanisms of femtosecond laser-induced refractive index modification of poly(methyl methacrylate)

The mechanisms of refractive index change in poly(methyl methacrylate) by frequency doubled femtosecond laser pulses are investigated. It is demonstrated that positive refractive index modificaton can be caused by a combination of depolymerization and crosslinking