Methyl methacrylate, addition

Rogalewicz, Voelkel [32] Poly(methyl methacrylate) thermal degradation Methyl methacrylate, additives PDMS... 

The RAFT-CLD-T technique was exemplified on styrene and later successfully mapped the chain length dependence of ki for methyl acrylate (MA), butyl acrylate,f dodecyl acryl-ate ° and methyl methacrylate. Additionally, the simultaneous dependence of kt on radical size and monomer conversion was mapped using the RAFT-CLD-T methodology for and vinyl acet-... 

In the ATRP of methyl methacrylate, addition of an excess tricyclohexylphosphine to the reaction mixture (up to 10 equiv. PCy3 relative to RuCl2(=CHPh)(PCy3)2) only slightly decreased the polymerisation activity of the catalyst (Table 3). 

The monomers used are second generation petrochemical products. The polymethacrylates are in fact copolymers based on methyl methacrylate and up to C20 molecular weight alcohol methacrylate. The properties of the additive are controlled based on the molecular ratio of these different monomers and their molecular weight. 

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. 

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). 

Acryhc stmctural adhesives have been modified by elastomers in order to obtain a phase-separated, toughened system. A significant contribution in this technology has been made in which acryhc adhesives were modified by the addition of chlorosulfonated polyethylene to obtain a phase-separated stmctural adhesive (11). Such adhesives also contain methyl methacrylate, glacial methacrylic acid, and cross-linkers such as ethylene glycol dimethacrylate [97-90-5]. The polymerization initiation system, which includes cumene hydroperoxide, N,1S7-dimethyl- -toluidine, and saccharin, can be apphed to the adherend surface as a primer, or it can be formulated as the second part of a two-part adhesive. Modification of cyanoacrylates using elastomers has also been attempted copolymers of acrylonitrile, butadiene, and styrene ethylene copolymers with methylacrylate or copolymers of methacrylates with butadiene and styrene have been used. However, because of the extreme reactivity of the monomer, modification of cyanoacrylate adhesives is very difficult and material purity is essential in order to be able to modify the cyanoacrylate without causing premature reaction. 

Transesterification of methyl methacrylate with the appropriate alcohol is often the preferred method of preparing higher alkyl and functional methacrylates. The reaction is driven to completion by the use of excess methyl methacrylate and by removal of the methyl methacrylate—methanol a2eotrope. A variety of catalysts have been used, including acids and bases and transition-metal compounds such as dialkjitin oxides (57), titanium(IV) alkoxides (58), and zirconium acetoacetate (59). The use of the transition-metal catalysts allows reaction under nearly neutral conditions and is therefore more tolerant of sensitive functionality in the ester alcohol moiety. In addition, transition-metal catalysts often exhibit higher selectivities than acidic catalysts, particularly with respect to by-product ether formation. 

Until 1982, almost all methyl methacrylate produced woddwide was derived from the acetone cyanohydrin (C-3) process. In 1982, Nippon Shokubai Kagaku Kogyo Company introduced an isobutylene-based (C-4) process, which was quickly followed by Mitsubishi Rayon Company in 1983 (66). Japan Methacryhc Monomer Company, a joint venture of Nippon Shokubai and Sumitomo Chemical Company, introduced a C-4-based plant in 1984 (67). Isobutylene processes are less economically attractive in the United States where isobutylene finds use in the synthesis of methyl /i / butyl ether, a pollution-reducing gasoline additive. BASF began operation of an ethylene-based (C-2) plant in Ludwigshafen, Germany, in 1990, but favorable economics appear to be limited to conditions unique to that site. 

The uniqueness of methyl methacrylate as a plastic component accounts for its industrial use in this capacity, and it far exceeds the combined volume of all of the other methacrylates. In addition to plastics, the various methacrylate polymers also find appHcation in sizable markets as diverse as lubricating oil additives, surface coatings (qv), impregnates, adhesives (qv), binders, sealers (see Sealants), and floor poHshes. It is impossible to segregate the total methacrylate polymer market because many of the polymers produced are copolymers with acrylates and other monomers. The total 1991 production capacity of methyl methacrylate in the United States was estimated at 585,000 t/yr. The worldwide production in 1991 was estimated at about 1,785,000 t/yr (3). 

Plastic Sheet. Poly(methyl methacrylate) plastic sheet is manufactured in a wide variety of types, including cleat and colored transparent, cleat and colored translucent, and colored semiopaque. Various surface textures ate also produced. Additionally, grades with improved weatherabiUty (added uv absorbers), mat resistance, crazing resistance, impact resistance, and flame resistance ate available. Selected physical properties of poly(methyl methacrylate) sheet ate Hsted in Table 12 (102). 

Methyl methacrylate is often used in combination with styrene to improve light transmission and uv stabiUty in fiame-retardant glazing appHcations. Phosphate ester (triethyl phosphate) additives are also included to supplement fiame-retardant efficiency benzophenone uv stabilizers are required to prevent yellowing of these uv-sensitive resins. 

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... 

Additional areas for growth are expected to be ia copper leaching, caprolactam, pulp and paper, methyl methacrylate, and batteries (144). 

Modifications of epichlorohydrin elastomers by radical-induced graft polymeri2ation have been reported. Incorporated monomers include styrene and acrylonitrile, styrene, maleic anhydride, vinyl acetate, methyl methacrylate, and vinyHdene chloride (81), acryHc acid (82), and vinyl chloride (81,83,84). When the vinyl chloride-modified epichlorohydrin polymers were used as additives to PVC, impact strength was improved (83,84). 

In addition to poly(methyl methacrylate) plastics and polyacrylonitrile fibres, acrylic polymers find widespread use. First introduced in 1946, acrylic rubbers have become established as important special purpose rubbers with a useful combination of oil and heat resistance. Acrylic paints have become widely accepted particularly in the car industry whilst very interesting reactive adhesives, including the well-known super-glues are also made from acrylic polymers. 

Poly(methyl methacrylate) may be blended with a number of additives. Of these the most important are dyes and pigments and these should be stable to both processing and service conditions. Two particular requirements are, firstly, that when used in castings they should not affect the polymerisation reaction and, secondly, that they should have good weathering resistance. 

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. 

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