Polystyrene methyl methacrylate

The polymer types shown are linear polystyrene, two types of branched polystyrene (methyl methacrylate), poly (vinyl chloride), poly butadiene poly (phenyl soiloxane), and two types of copolymer. 

Polymer Selection. The polymer was selected on the basis of observations using salicylic acid-salicylate as analyte. The following organic polymers were examined polystyrene, methyl methacrylate-ethyl acrylate, Teflon, silicone rubber, PVC, and polyester. Ten-millimolar salicylic acid in 0.01 M HC1 was first extracted for 30 s and then back extracted with 0.1 M NaOH. Peak currents for back extractants (nA) were as follows PVC, 1780 methyl methacrylate-ethyl... 

Applying this method to the system polystyrene/methyl methacrylate, block copolymers containing 20—30% styrene have been prepared the systems polyvinyl acetate/styrene and polyvinyl acetate/ethyl chloroacrylate afford block copolymers containing respectively 40 and 82% vinyl acetate 204). In contrast, the polystyrene prepared using phthalyl polyperoxide was unable to initiate the polymerization of vinyl acetate or vinylpyrrolidone, likely on account of the difference in stability of the concerned radicals. 

Another polymer that has been very successful in blends with SBC is polystyrene-methyl methacrylate (SMMA), a styrene acrylic copolymer. Compared with SBC, SMMA offers significantly higher stiffness, surface hardness and temperature resistance. The refractive index of these copolymers can be... 

Low Density Polyethylene High Density Polyethylene P o1ypropy1ene Polyvinyl Chloride Polyacetal Polystyrene Expanded Polystyrene Methyl methacrylate butadiene styrene terpolymer Phenol Formaldehyde Melamine Formaldehyde Urea Formaldehyde On-stream mid-1993... 

Medium-impact-strength polystyrene Methyl methacrylate (monomer)... 

The systems poly(methyl methacrylate)-styrene and polystyrene-methyl methacrylate were studied by Watson and co-workers [111]. The composition of these interpolymers is shown in Fig. 5.25 [111]. In the polystyrene-methyl methacrylate system, 53% of the original polymer remained as homopolymer at the end of the reaction. Homopoly(methyl methacrylate) was formed during the early stages of reaction (40 and 91% of the polymerized monomer after 80 and 95% conversion, respectively). The amount of block polymer reached a maximum of only 42% of the product. 

The chemical composition and molecular weight distribution of high conversion polystyrene - methyl methacrylate (54 - 85% methyl methacrylate) has been determined by liquid adsorption and size exclusion chromatography. ... 

Figure Bl.19.30. Height and friction images of a spin-cast polystyrene-poly(methyl methacrylate) blend obtained with (a) gold and (b) silica probes under perfluorodecalin. Note the reversal of frictional contrast and the high spatial resolution. (Taken from [142], figure 7.)...

Combination and disproportionation are competitive processes and do not occur to the same extent for all polymers. For example, at 60°C termination is virtually 100% by combination for polyacrylonitrile and 100% by disproportionation for poly (vinyl acetate). For polystyrene and poly (methyl methacrylate), both reactions contribute to termination, although each in different proportions. Each of the rate constants for termination individually follows the Arrhenius equation, so the relative amounts of termination by the two modes is given by... 

Figure 9.17 Plot of log [i ]M versus retention volume for various polymers, showing how different systems are represented by a single calibration curve when data are represented in this manner. The polymers used include linear and branched polystyrene, poly(methyl methacrylate), poly(vinyl chloride), poly(phenyl siloxane), polybutadiene, and branched, block, and graft copolymers of styrene and methyl methacrylate. [From Z. Grubisec, P. Rempp, and H. Benoit, Polym. Lett. 5 753 (1967), used with permission of Wiley.]...

In 1954 the surface fluorination of polyethylene sheets by using a soHd CO2 cooled heat sink was patented (44). Later patents covered the fluorination of PVC (45) and polyethylene bottles (46). Studies of surface fluorination of polymer films have been reported (47). The fluorination of polyethylene powder was described (48) as a fiery intense reaction, which was finally controlled by dilution with an inert gas at reduced pressures. Direct fluorination of polymers was achieved in 1970 (8,49). More recently, surface fluorinations of poly(vinyl fluoride), polycarbonates, polystyrene, and poly(methyl methacrylate), and the surface fluorination of containers have been described (50,51). Partially fluorinated poly(ethylene terephthalate) and polyamides such as nylon have excellent soil release properties as well as high wettabiUty (52,53). The most advanced direct fluorination technology in the area of single-compound synthesis and synthesis of high performance fluids is currently practiced by 3M Co. of St. Paul, Minnesota, and by Exfluor Research Corp. of Austin, Texas. 

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). 

Other Polymers. Besides polycarbonates, poly(methyl methacrylate)s, cycfic polyolefins, and uv-curable cross-linked polymers, a host of other polymers have been examined for their suitabiUty as substrate materials for optical data storage, preferably compact disks, in the last years. These polymers have not gained commercial importance polystyrene (PS), poly(vinyl chloride) (PVC), cellulose acetobutyrate (CAB), bis(diallylpolycarbonate) (BDPC), poly(ethylene terephthalate) (PET), styrene—acrylonitrile copolymers (SAN), poly(vinyl acetate) (PVAC), and for substrates with high resistance to heat softening, polysulfones (PSU) and polyimides (PI). 

Examples of the two macromolecular nomenclature systems are as foUows. For source-based names for homopolymers and copolymers polyacrylonitrile, poly(methyl methacrylate), poly(acrylainide- (9-vinylpyrroHdinone), polybutadiene- /oi / -polystyrene, and poly(propyl... 

Interpenetrating networks of DMPPO and polymers such as polystyrene, polybutadiene, poly(urethane acrylate), and poly(methyl methacrylate) have been prepared by cross-linking solutions of DMPPO containing bromomethyl groups with ethylenediamine in the presence of the other polymer (68). 

Fig. 4. Comparative thermogravimetric analyses of polymers in nitrogen A, poly(vinyl chloride) B, poly(methyl methacrylate) C, polystyrene D,...

In the eady 1920s, experimentation with urea—formaldehyde resins [9011-05-6] in Germany (4) and Austria (5,6) led to the discovery that these resins might be cast into beautiful clear transparent sheets, and it was proposed that this new synthetic material might serve as an organic glass (5,6). In fact, an experimental product called PoUopas was introduced, but lack of sufficient water resistance prevented commercialization. Melamine—formaldehyde resin [9003-08-1] does have better water resistance but the market for synthetic glass was taken over by new thermoplastic materials such as polystyrene and poly(methyl methacrylate) (see Methacrylic polya rs Styrene plastics). 

Fig. 15. Oxygen permeability versus 1/specific free volume at 25 °C (30). 1. Polybutadiene 2. polyethylene (density 0.922) 3. polycarbonate 4. polystyrene 5. styrene-acrylonitrile 6. poly(ethylene terephthalate) 7. acrylonitrile barrier polymer 8. poly(methyl methacrylate) 9. poly(vinyl chloride) 10. acrylonitrile barrier polymer 11. vinyUdene chloride copolymer 12. polymethacrylonitrile and 13. polyacrylonitrile. See Table 1 for unit conversions.

In general, the azo colors are useful for coloring polystyrene, phenoHcs, and rigid poly(vinyl chloride). Many are compatible with poly(methyl methacrylate), but in this case the weatherabiUty of the resin far exceeds the life of the dyes. Among the more widely used azo dyes (qv) are Solvent Yellows 14 and 72 Orange 7 and Reds 1, 24, and 26. 

The anthraquinones are useful in acrylics and are compatible with polystyrene and ceUulosics. Solvent Red 111 has a special affinity for poly(methyl methacrylate) as the red in automobile taillights exposure for a year in Florida or Arizona produces only a very slight darkening. Acid types are usehil for phenohcs (see Dyes, anthraquinone). 

The acetone supply is strongly influenced by the production of phenol, and so the small difference between total demand and the acetone suppHed by the cumene oxidation process is made up from other sources. The largest use for acetone is in solvents although increasing amounts ate used to make bisphenol A [80-05-7] and methyl methacrylate [80-62-6]. a-Methylstyrene [98-83-9] is produced in controlled quantities from the cleavage of cumene hydroperoxide, or it can be made directly by the dehydrogenation of cumene. About 2% of the cumene produced in 1987 went to a-methylstyrene manufacture for use in poly (a-methylstyrene) and as an ingredient that imparts heat-resistant quaUties to polystyrene plastics. 

Acrylic Resins. The first synthetic polymer denture material, used throughout much of the 20th century, was based on the discovery of vulcanised mbber in 1839. Other polymers explored for denture and other dental uses have included ceUuloid, phenolformaldehyde resins, and vinyl chloride copolymers. Polystyrene, polycarbonates, polyurethanes, and acryHc resins have also been used for dental polymers. Because of the unique combination of properties, eg, aesthetics and ease of fabrication, acryHc resins based on methyl methacrylate and its polymer and/or copolymers have received the most attention since their introduction in 1937. However, deficiencies include excessive polymerization shrinkage and poor abrasion resistance. Polymers used in dental appHcation should have minimal dimensional changes during and subsequent to polymerization exceUent chemical, physical, and color stabiHty processabiHty and biocompatibiHty and the abiHty to blend with contiguous tissues. 

In principle, A can be any polymer normally regarded as a hard thermoplastic, eg, polystyrene, poly(methyl methacrylate), or polypropylene, and B can be any polymer normally regarded as elastomeric, eg, polyisoprene, polybutadiene, polyisobutylene, or polydimethylsiloxane (Table 2). 

The decade 1930-1940 saw the initial industrial development of four of today s major thermoplastics polystyrene, poly(vinyl chloride) (PVC), the polyolefins and poly(methyl methacrylate). Since all these materials can be considered formally as derivatives of ethylene they have, in the past, been referred to as ethenoid plastics however, the somewhat inaccurate term vinyl plastics is now usually preferred. 

In these cases the monomer is converted into polymer, and no side products are formed. This approach is used with the major thermoplastics materials (Figure 2.2) such as polyethylene (a polymer of ethylene), polystyrene (a polymer of styrene) and poly(methyl methacrylate) (a polymer of methyl methacrylate). 

The melt viscosity of a polymer at a given temperature is a measure of the rate at which chains can move relative to each other. This will be controlled by the ease of rotation about the backbone bonds, i.e. the chain flexibility, and on the degree of entanglement. Because of their low chain flexibility, polymers such as polytetrafluoroethylene, the aromatic polyimides, the aromatic polycarbonates and to a less extent poly(vinyl chloride) and poly(methyl methacrylate) are highly viscous in their melting range as compared with polyethylene and polystyrene. 

Poly(methyl methacrylate) is a good electrical insulator for low-frequency work, but is inferior to such polymers as polyethylene and polystyrene, particularly at high frequencies. The influence of temperature and frequency on the dielectric constant is shown in Figure 15.9. 

As with other rigid amorphous thermoplastic polymers such as PVC and polystyrene (see the next chapter) poly(methyl methacrylate) is somewhat brittle and, as with PVC and polystrene, efforts have been made to improve the toughness by molecular modification. Two main approaches have been used, both of which have achieved a measure of success. They are copolymerisation of methyl methacrylate with a second monomer and the blending of poly(methyl methacrylate) with a rubber. The latter approach may also involve some graft copolymerisation. 

Following the success in blending rubbery materials into polystyrene, styrene-acrylonitrile and PVC materials to produce tough thermoplastics the concept has been used to produce high-impact PMMA-type moulding compounds. These are two-phase materials in which the glassy phase consists of poly(methyl methacrylate) and the rubbery phase an acrylate polymer, usually poly(butyl acrylate Commercial materials of the type include Diakon MX (ICI), Oroglas... 

The important features of rigidity and transparency make the material competitive with polystyrene, cellulose acetate and poly(methyl methacrylate) for a number of applications. In general the copolymer is cheaper than poly(methyl methacrylate) and cellulose acetate, tougher than poly(methyl methacrylate) and polystyrene and superior in chemical and most physical properties to polystyrene and cellulose acetate. It does not have such a high transparency or such food weathering properties as poly(methyl methacrylate). As a result of these considerations the styrene-acrylonitrile copolymers have found applications for dials, knobs and covers for domestic appliances, electrical equipment and car equipment, for picnic ware and housewares, and a number of other industrial and domestic applications with requirements somewhat more stringent than can be met by polystyrene. 

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