Methacrylate polymers poly

Beaded methacrylate polymers, poly(hydroxyethylmethacrylate), Spheron, Separon (29), and poly(glycidylmethacrylate), Eupergin (30,31), are studied extensively at the Czechoslovak Academy of Macromolecular Sciences. An addition to this type of support is poly(oxyethylene-dimethacrylate) (32). Heitz et al. (33) described the preparation of beaded poly(methylacrylates) cross-linked with ethanedimethacrylates. 

The class of compounds called polyesters consists of aU heterochain macromolecular compounds that possess repeat carboxylate ester groups in the backbones. This excludes all polymers with ester groups located as pendant groups, like acrylic and methacrylic polymers, poly(vinyl esters), and esters of cellulose, or starch. What remains, however, is still a large group of polymeric materials that can be subdivided into saturated and unsaturated polyesters. 

Acrylate and Methacrylate Polymers. Poly(ethyl acrylate) and poly(butyl acrylate) solutions and emulsions are important raw materials for pressure-sensitive adhesives. Copolymers of various esters, which give films of tailor-made hardness and which may additionally contain functional groups (carboxyl, amide, amino, methylol, hydroxyl), are used for pressure-sensitive adhesives to improve the adhesion properties or to enable the adhesive layer to be cross-hnked to a limited extent. 

Another type of synthetic polymer-based chiral stationary phase is formed when chiral catalyst are used to initiate the polymerisation. In the case of poly(methyl methacrylate) polymers, introduced by Okamoto, the chiraUty of the polymer arises from the heUcity of the polymer and not from any inherent chirahty of the individual monomeric subunits (109). Columns of this type (eg, Chiralpak OT) are available from Chiral Technologies, Inc., or J. T. Baker Inc. 

Poly(acrylic acid) and Poly(methacrylic acid). Poly(acryHc acid) (8) (PAA) may be prepared by polymerization of the monomer with conventional free-radical initiators using the monomer either undiluted (36) (with cross-linker for superadsorber appHcations) or in aqueous solution. Photochemical polymerization (sensitized by benzoin) of methyl acrylate in ethanol solution at —78° C provides a syndiotactic form (37) that can be hydrolyzed to syndiotactic PAA. From academic studies, alkaline hydrolysis of the methyl ester requires a lower time than acid hydrolysis of the polymeric ester, and can lead to oxidative degradation of the polymer (38). Po1y(meth acrylic acid) (PMAA) (9) is prepared only by the direct polymerization of the acid monomer it is not readily obtained by the hydrolysis of methyl methacrylate. 

Most of the polymer s characteristics stem from its molecular stmcture, which like POE, promotes solubiUty in a variety of solvents in addition to water. It exhibits Newtonian rheology and is mechanically stable relative to other thermoplastics. It also forms miscible blends with a variety of other polymers. The water solubiUty and hot meltable characteristics promote adhesion in a number of appHcations. PEOX has been observed to promote adhesion comparable with PVP and PVA on aluminum foil, cellophane, nylon, poly(methyl methacrylate), and poly(ethylene terephthalate), and in composite systems improved tensile strength and Izod impact properties have been noted. 

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). 

Optics. Good optical properties and low thermal resistance make poly(methyl methacrylate) polymers well suited for use as plastic optical fibers. The manufacturing methods and optical properties of the fibers have been reviewed (124) (see Fiber optics). Methods for the preparation of Fresnel lenses and a Fresnel lens film have been reported (125,126). Compositions and methods for the industrial production of cast plastic eyeglass lenses are available (127). 

Poly(methyl methacrylate) and poly(vinyl acetate) precipitate from the resin solution as it cures. This mechanism offsets the contraction in volume as the polyester resin cross-links, resulting in a nonshrinking thermoset. Other polymer additives such as poly(butylene adipate) provide similar shrinkage... 

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.

Polymethacrylates. Poly(methyl methacrylate) [9011-14-7] is a thermoplastic. Itis the acryUc resin most used in building products, frequendy as a blend or copolymer with other materials to improve its properties. The monomer is polymerized either by bulk or suspension processes. Eor glazing material, its greatest use, only the bulk process is used. Sheets are prepared either by casting between glass plates or by extmsion of pellets through a sHt die. This second method is less expensive and more commonly used. Peroxide or azo initiators are used for the polymerization (see Methacrylic polymers). 

A large number of methacrylate polymers have been prepared in addition to poly(methyl methacrylate). In many respects the properties of these materials are analogous to those of the polyolefins described in Chapter 8. 

A number of higher n-alkyl methacrylate polymers have found commercial usage. The poly-(n-butyl-), poly-(n-octyl-) and poly-(n-nonyl methacrylate)s have found use as leathering finishes whilst polyflauryl methacrylate) has become useful as a pour-point depressant and improver of viscosity temperature characteristics of lubricating oils. 

Davis, P. A. Nicolais, L., Ambrosio, L., and Huang, S. J., Synthesis and characterization of semi-interpenetrating polymer networks of poly(2-hydroxyethyl methacrylate) and poly(capro-lactone), Polym. Mater. Sci. Eng., 56, 536-540, 1987. 

N Thomas, AH Windle. Transport of methanol in poly(methyl methacrylate). Polymer 19 255-265, 1978. 

D Biren, BG Kabra, SH Gehrke. Effect of initial sample anisotropy on the solvent sorption kinetics of glassy poly(2-hydroxyethyl methacrylate). Polymer 33 554-561, 1992. 

We can divide commodity plastics into two classes excellent and moderate insulators. Polymers that have negligible polar character, typically those containing only carbon-carbon and carbon-hydrogen bonds, fall into the first class. This group includes polyethylene, polypropylene, and polystyrene. Polymers made from polar monomers are typically modest insulators, due to the interaction of their dipoles with electrical fields. We can further divide moderate insulators into those that have dipoles that involve backbone atoms, such as polyvinyl chloride and polyamides, and those with polar bonds remote from the backbone, such as poly(methyl methacrylate) and poly(vinyl acetate). Dipoles involving backbone atoms are less susceptible to alignment with an electrical field than those remote from the backbone. 

Methyl and ethyl methacrylate polymers, although extensively used in Industry, do not possess the solubility characteristics (low polarity) that would make them appropriate for use over traditional oil paintings and other organic-based museum objects that might be sensitive to polar solvents such as alcohols, ketones and esters. Poly(n-butyl methacrylate), offered as an artists varnish in the late 1930 s, did not become widely accepted in the war-disrupted decade that followed. Accordingly, early in 1951, our laboratory began a detailed study of the higher alkyl methacrylate polymers for potential use as picture varnishes (1). 

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