PMMA

PMMA is the most common member of the acrylic family and widely known as the ICI trade name of Perspex . Acrylic has excellent transparency and no appreciable yellowing under sunlight. They are therefore used in the construction industry and in the electrical industry for lighting systems and lenses. 

All shear strengths are given as guidelines only and may vary considerably depending on grade of plastic, fillers, surface finish, etc. 

Acrylics are not usually recommended for high-temperature applications but they do 

Acrylics can be bonded with most adhesives and in these trials [2] cyanoacrylates (without primer) and UV-curing acrylics gave best results (Table 2.11). The silicone adhesive did not show good strengths. 

POM is widely known as acetal and a well-known trade name is Delrin , manufactured by DuPont. This is a popular engineering plastic to replace parts that might otherwise be manufactured from metals. It is generally easy to machine and therefore makes for a good engineering plastic for small batch production or prototype applications. 

The measurement cell provided with the Laser Zee Meter 500 (Pen Kem) is made of PMMA. 

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Mixtures of polymers at surfaces provide the interesting possibility of exploring polymer miscibility in two dimensions. Baglioni and co-workers [17] have shown that polymers having the same orientation at the interface are compatible while those having different orientations are not. Some polymers have their hydrophobic portions parallel to the surface, while others have a perpendicular disposition. The surface orientation effect is also present in mixtures of poly(methyl methacrylate), PMMA, and fatty acids. 

Figure Bl.22.11. Near-field scanning optical microscopy fluorescence image of oxazine molecules dispersed on a PMMA film surface. Each protuberance in this three-dimensional plot corresponds to the detection of a single molecule, the different intensities of those features being due to different orientations of the molecules. Sub-diffraction resolution, in this case on the order of a fraction of a micron, can be achieved by the near-field scaiming arrangement. Spectroscopic characterization of each molecule is also possible. (Reprinted with pennission from [82]. Copyright 1996 American Chemical Society.)...

Figure Cl.5.3. Near-field fluorescence image 4.5 p.m square) of single oxazine 720 molecules dispersed on die surface of a PMMA film. Each peak (fwhm 100 nm) is due to a single molecule. The different intensities are due to different molecular orientations and spectra. Reprinted widi pennission from Xie 11221. Copyright 1996 American Chemical Society.

Figure Cl.5.4. Comparison of near-field and far-field fluorescence images, spectra and lifetimes for the same set of isolated single molecules of a carbocyanine dye at a PMMA-air interface. Note the much higher resolution of the near-field image. The spectmm and lifetime of the molecule indicated with the arrow were recorded with near-field excitation and with far-field excitation at two different excitation powers. Reproduced with pennission from Trautman and Macklin [125].

Single molecules also have promise as probes for local stmcture when doped into materials tliat are tliemselves nonfluorescent. Rlrodamine dyes in botli silicate and polymer tliin films exliibit a distribution of fluorescence maxima indicative of considerable heterogeneity in local environments, particularly for the silicate material [159]. A bimodal distribution of fluorescence intensities observed for single molecules of crystal violet in a PMMA film has been suggested to result from high and low viscosity local sites witliin tire polymer tliat give rise to slow and fast internal conversion, respectively [160]. 

Anotlier model system consists of polymetliylmetliacrylate (PMMA) latex, stabilized in organic solvents by a comb polymer, consisting of a PMMA backbone witli poly-12-hydroxystearic acid (PHSA) chains attached to it [10]. The PHSA chains fonn a steric stabilization layer at tire surface (see section C2.6.4). Such particles can approach tire hard-sphere model very well [111. 

Poly(methyl methacrylate) (PMMA) Ethylene-chlorotrifluoroethylene copolymer... 

Acrylics. Acetone is converted via the intermediate acetone cyanohydrin to the monomer methyl methacrylate (MMA) [80-62-6]. The MMA is polymerized to poly(methyl methacrylate) (PMMA) to make the familiar clear acryUc sheet. PMMA is also used in mol ding and extmsion powders. Hydrolysis of acetone cyanohydrin gives methacrylic acid (MAA), a monomer which goes direcdy into acryUc latexes, carboxylated styrene—butadiene polymers, or ethylene—MAA ionomers. As part of the methacrylic stmcture, acetone is found in the following major end use products acryUc sheet mol ding resins, impact modifiers and processing aids, acryUc film, ABS and polyester resin modifiers, surface coatings, acryUc lacquers, emulsion polymers, petroleum chemicals, and various copolymers (see METHACRYLIC ACID AND DERIVATIVES METHACRYLIC POLYMERS). 

The cured polymers are hard, clear, and glassy thermoplastic resins with high tensile strengths. The polymers, because of their highly polar stmcture, exhibit excellent adhesion to a wide variety of substrate combinations. They tend to be somewhat britde and have only low to moderate impact and peel strengths. The addition of fillers such as poly (methyl methacrylate) (PMMA) reduces the brittleness somewhat. Newer formulations are now available that contain dissolved elastomeric materials of various types. These mbber-modifted products have been found to offer adhesive bonds of considerably improved toughness (3,4). 

Unlike most crystalline polymers, PVDF exhibits thermodynamic compatibiUty with other polymers (133). Blends of PVDF and poly(methyl methacrylate) (PMMA) are compatible over a wide range of blend composition (134,135). SoHd-state nmr studies showed that isotactic PMMA is more miscible with PVDF than atactic and syndiotactic PMMA (136). MiscibiUty of PVDF and poly(alkyl acrylates) depends on a specific interaction between PVDF and oxygen within the acrylate and the effect of this interaction is diminished as the hydrocarbon content of the ester is increased (137). Strong dipolar interactions are important to achieve miscibility with poly(vinyhdene fluoride) (138). PVDF blends are the object of many papers and patents specific blends of PVDF and acryflc copolymers have seen large commercial use. 

PMMA-impregnated sol—gel-derived siUca gels have also been examined (54). Long-wave uv illumination was employed in addition to benzoyl peroxide for PMMA polymerization. This method prohibited the degradation of the siUca xerogel from moisture adsorption and desorption. Overall the material behaved more like bulk PMMA than bulk siUca, with the exception of hardness. 

Examples of photothermoplasts include polyacrylates, polyacrylamides, polystyrenes, polycarbonates, and their copolymers (169). An especially well-re searched photothermoplast is poly(methyl methacrylate) (PMMA), which is blended with methyl methacrylate (MMA) or styrene as a monomer, and titanium-bis(cyclopentadienyl) as a photoinitiator (170). 

New PHB materials are composed of Zn-tetraben2oporphyrin—aromatic cyanide—poly (methyl methacrylate) (180) or of tetraphenylporphyrin derivatives dispersed in polymer matrices such as PMMA and polyethylene (181). A survey of such materials has been given (181). 

Poly(methyl methacrylate). PMMA offers distinct advantages over BPA-PC with respect to significandy lower birefringence, higher modulus, and lower costs, but has not been successhil as a material for audio CDs and CD-ROM as well as a substrate material for WORM and EOD disks because of its high water absorption (which makes it prone to warp) and its unsuitabiUty for metallising, and less so because of its low resistance to... 

More recently, test products were created of a blend of PMMA with a phenyl-substituted methacrylate these products have a glass-transition temperature of around 125°C, a significantly reduced water absorption compared to pure PMMA of about 0.32%, but also a higher birefringence (a stress-optic coefficient of 5.2 X 10 , compared with 0.3 X 10 for PMMA and 6.8 x 10 for BPA-PC). 

Table 9 compares the most important properties of substrate materials based on BPA-PC, PMMA, and CPO (three different products) (216,217). The future will prove if the current disadvantages of CPO against BPA-PC regarding warp, processibiUty (melt viscosity), and especially cost can be alleviated. CycHc polyolefins (CPO) and, especially cycloolefin copolymers (COC) (218) and blends of cycloolefin copolymers with suitable engineering plastics have the potential to be interesting materials for substrate disks for optical data storage. 

Special, uv-curable epoxy resins (qv) for substrate disks for optical data storage (Sumitomo BakeHte, Toshiba) excel by means of their very low birefringence (<5 nm/mm) and high Young s modulus. Resistance to heat softening and water absorption are similar to BPA-PC, but impact resistance is as low as that of PMMA. 

Reduction or even complete compensation of birefringence by mixing polymers with positive birefringence (PC, PVC, PETP, PPE, PVDF, etc) with polymers with negative birefringence (PMMA, PS, PAN, etc) has been the consistent strategy. 

The TPX experimental product of Mitsubishi Petrochemical Ind. (221) is an amorphous, transparent polyolefin with very low water absorption (0.01%) and a glass-transition temperature comparable to that of BPA-PC (ca 150°C). Birefringence (<20 nm/mm), flexural modulus, and elongation at break are on the same level as PMMA (221). The vacuum time, the time in minutes to reach a pressure of 0.13 mPa (10 torr), is similarly short like that of cychc polyolefins. Typical values of TPX are fisted in Table 11. A commercial application of TPX is not known as of this writing. 

Fig. 26. Qualitative compatison of substrate materials for optical disks (187) An = birefringence IS = impact strength BM = bending modulus HDT = heat distortion temperature Met = metallizability WA = water absorption Proc = processibility. The materials are bisphenol A—polycarbonate (BPA-PC), copolymer (20 80) of BPA-PC and trimethylcyclohexane—polycarbonate (TMC-PC), poly(methyl methacrylate) (PMMA), uv-curable cross-linked polymer (uv-DM), cycHc polyolefins (CPO), and, for comparison, glass.

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