Methyl methacrylate polymers properties

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). 

The photophysical properties and photostability of oxazine dye molecules for use in luminescent solar concentrators have been reported. Tests have shown that the optical efficiencies of luminescent solar concentrators prepared using a single dye in a liquid methyl methacrylate polymer are as efficient as those fabricated using the same single dye dissolved in methyl methacrylate, and which is then thermally polymerised. ... 

Table 15.1 Some properties of methyl methacrylate polymers...

Nakason, C., Saiwaree, S., Tatun, S., and Kaesaman, A. 2006. Rheological, thermal and morphological properties of maleated natural rubber and its reactive blending with poly (methyl methacrylate). Polymer Testing 25(5) 656-667. 

FOX Fox, T.G., Properties of dilute polymer solutions 111. Intrinsic viscosity/tempeiature relationships for conventional poly methyl methacrylate. Polymer, 3, 111, 1962. 

P. A. Botto, R. A. Duckett, and I. M. Ward, The Yield and Thermoelastic Properties of Oriented Poly(Methyl-Methacrylate) , Polymer 28, 257-262 (1987). 

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. 

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. 

T is the glass-transition temperature at infinite molecular weight and is the number average molecular weight. The value of k for poly(methyl methacrylate) is about 2 x 10 the value for acrylate polymers is approximately the same (9). A detailed discussion on the effect of molecular weight on the properties of a polymer may be found in Reference 17. 

A review covers the preparation and properties of both MABS and MBS polymers (75). Literature is available on the grafting of methacrylates onto a wide variety of other substrates (76,77). Typical examples include the grafting of methyl methacrylate onto mbbers by a variety of methods chemical (78,79), photochemical (80), radiation (80,81), and mastication (82). Methyl methacrylate has been grafted onto such substrates as cellulose (83), poly(vinyl alcohol) (84), polyester fibers (85), polyethylene (86), poly(styrene) (87), poly(vinyl chloride) (88), and other alkyl methacrylates (89). 

The dynamic mechanical properties of VDC—VC copolymers have been studied in detail. The incorporation of VC units in the polymer results in a drop in dynamic modulus because of the reduction in crystallinity. However, the glass-transition temperature is raised therefore, the softening effect observed at room temperature is accompanied by increased brittleness at lower temperatures. These copolymers are normally plasticized in order to avoid this. Small amounts of plasticizer (2—10 wt %) depress T significantly without loss of strength at room temperature. At higher levels of VC, the T of the copolymer is above room temperature and the modulus rises again. A minimum in modulus or maximum in softness is usually observed in copolymers in which T is above room temperature. A thermomechanical analysis of VDC—AN (acrylonitrile) and VDC—MMA (methyl methacrylate) copolymer systems shows a minimum in softening point at 79.4 and 68.1 mol % VDC, respectively (86). 

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). 

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. 

The properties of three types of poly(methyl methacrylate) (sheet based on high molecular weight polymer, lower molecular weight injection moulding material and a one-time commercial copolymer) are given in Table 15.1. 

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. 

An example of this improvement in toughness can be demonstrated by the addition of Vamac B-124, an ethylene/methyl acrylate copolymer from DuPont, to ethyl cyanoacrylate [24-26]. Three model instant adhesive formulations, a control without any polymeric additive (A), a formulation with poly(methyl methacrylate) (PMMA) (B), and a formulation with Vamac B-124 (C), are shown in Table 4. The formulation with PMMA, a thermoplastic which is added to modify viscosity, was included to determine if the addition of any polymer, not only rubbers, could improve the toughness properties of an alkyl cyanoacrylate instant adhesive. To demonstrate an improvement in toughness, the three formulations were tested for impact strength, 180° peel strength, and lapshear adhesive strength on steel specimens, before and after thermal exposure at 121°C. 

An effective method of NVF chemical modification is graft copolymerization [34,35]. This reaction is initiated by free radicals of the cellulose molecule. The cellulose is treated with an aqueous solution with selected ions and is exposed to a high-energy radiation. Then, the cellulose molecule cracks and radicals are formed. Afterwards, the radical sites of the cellulose are treated with a suitable solution (compatible with the polymer matrix), for example vinyl monomer [35] acrylonitrile [34], methyl methacrylate [47], polystyrene [41]. The resulting copolymer possesses properties characteristic of both fibrous cellulose and grafted polymer. 

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