Poly monomer derivatives

Postsulfonation of polymers to form PEMs can lead to undesirable side reactions and may be hard to control on a repeatable basis. Synthesis of sulfonated macromolecules for use in PEMs by the direct reaction of sulfonated comonomers has gained attention as a rigorous method of controlling the chemical structure, acid content, and even molecular weight of these materials. While more challenging synthetically than postsulfonation, the control of the chemical nature of the polymer afforded by direct copolymerization of sulfonated monomers and the repeatability of the reactions allows researchers to gain a more systematic understanding of these materials properties. Sulfonated poly(arylene ether)s, sulfonated poly-(imide)s, and sulfonated poly(styrene) derivatives have been the most prevalent of the directly copolymerized materials. 

Ecoflex ES was commercialized by BASE in 2010 as a compound with poly(lactic acid) (PEA) (Ecovio ES see Sect. 4.2.2). Ecoflex ES is an aliphatic-aromatic polyester with a similar structure to that of Ecoflex E (see Eig. 3). However, through exchanging one of the monomers with a monomer derived from plant oil, the new Ecoflex ES is partly based on renewable resources. 

In addition to the dibenzodioxin reaction, the more classical polymerization reaction of imide formation has been used to form PIMs. Weber and co-workers [117, 118] firstly reported the synthesis of soluble poly(amide) and poly(imide) using monomers derived from 9,9 -spirobifluorene. Such a spirobifluorene generates a 90° kink per repeating imit and thus prevoits space-efficient chain packing, resulting in microporous materials with high surface areas. For example, by reacting 2,2 -diamino-9,9 -spirobifluorene (Fig. 5.15, Al) with pyromellitic dianhydride (PMDA) (Fig. 5.15, Bl), a soluble polymer with a BET surface area of 551 m g was obtained [118]. Binaphthalene-based polyimide was synthesized by Ritter et al. 

This monomer, derived from acetylene and carbazole, is used in the production of poly (n-vinylcarbazole). 

The synthesis of monomers derived from fatty acids incorporating end-functions susceptible to classical poly addition reactions has been revived recently and yielded interesting results. Vinyl oleate (VO) and vinyl linoleate (VL) were synthesised by a transvinylation reaction of the corresponding fatty acids with an excess of vinyl acetate (VAc) in bulk using a safe iridium-based catalyst instead of previously used mercury-based counterparts (which are not acceptable today because of safety concerns) [91]. Scheme 4.21 summarises this synthesis in the case of OA. 

Poly(lactic acid) (PLA) and starch are two promising candidates for biodegradable polymer blends since both materials are commercially available. PLA is a synthetic polymer produced from a natural monomer derived from starch, and of course starch is naturally abundant, which is derived from several plant forms [1-28],... 

Monomers derived from trimellitic anhydride, mainly V-carboxyphenyltrimel-litimides and V-(co-carboxyalkylene)trimellitimides have been also used many times as starting materials for the synthesis of poly (amide imide)s. These poly (amide imide)s have been traditionally prepared by low temperature solution polycondensation, from diamines and imide-diacid chlorides [182], but they have been also successfully synthesized by the phosphorylation method of direct polyamidation [184], from diamines and imide-diacids [185-188] as depicted in Scheme (36). Trimellitic acid imide (4-carboxyphthal-imide) has also been used for the preparation of poly(amide imide)s, by reaction with aliphatic and aromatic diamines in solution at moderate temperatures [189]. 

Vinyl-2-Pyrrolidone n (N-vinyl-2-pyrrolidone) A cyclic monomer derived from acetylene and formaldehyde, with the structure below. See Poly(l-Vinylpyrrolidone). 

COE and a COE-based cross-linker, that is, tris(cyclooct-4-en-l-yloxy)methylsilane (TCOMS). This development was guided by the idea that the polymer backbone of poly (COE)-derived materials consists of sec-allylic carbons and, therefore, presents a viable alternative to NBE-based systems. However, compared to NBE-based monomers, COEs are characterized by a significantly reduced ring strain, which makes the use of a more active initiator than the commonly used first-generation Grubbs initiator inevitable. These changes in monomer, cross-linker, and initiator required a comprehensive redesign of monolith synthesis. As a direct consequence of... 

Fig. 11-32 illustrates the difficulty in studying CPs in the solid state. Here the low-temperature, C MAS spectrum of undoped poly(azulene) is shown together with that of a monomer derivative [441]. The broad resonance for the polymer bespeaks delocalized charge or disordered polymer structure, but does not convey much additional information. 

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). 

Suitable protective coUoids for the preparation of acryhc suspension polymers include ceUulose derivatives, polyacrylate salts, starch, poly(vinyl alcohol), gelatin, talc, clay, and clay derivatives (95). These materials are added to prevent the monomer droplets from coalescing during polymerisation (110). Thickeners such as glycerol, glycols, polyglycols, and inorganic salts ate also often added to improve the quahty of acryhc suspension polymers (95). 

Emulsion Adhesives. The most widely used emulsion-based adhesive is that based upon poly(vinyl acetate)—poly(vinyl alcohol) copolymers formed by free-radical polymerization in an emulsion system. Poly(vinyl alcohol) is typically formed by hydrolysis of the poly(vinyl acetate). The properties of the emulsion are derived from the polymer employed in the polymerization as weU as from the system used to emulsify the polymer in water. The emulsion is stabilized by a combination of a surfactant plus a coUoid protection system. The protective coUoids are similar to those used paint (qv) to stabilize latex. For poly(vinyl acetate), the protective coUoids are isolated from natural gums and ceUulosic resins (carboxymethylceUulose or hydroxyethjdceUulose). The hydroHzed polymer may also be used. The physical properties of the poly(vinyl acetate) polymer can be modified by changing the co-monomer used in the polymerization. Any material which is free-radically active and participates in an emulsion polymerization can be employed. Plasticizers (qv), tackifiers, viscosity modifiers, solvents (added to coalesce the emulsion particles), fillers, humectants, and other materials are often added to the adhesive to meet specifications for the intended appHcation. Because the presence of foam in the bond line could decrease performance of the adhesion joint, agents that control the amount of air entrapped in an adhesive bond must be added. Biocides are also necessary many of the materials that are used to stabilize poly(vinyl acetate) emulsions are natural products. Poly(vinyl acetate) adhesives known as "white glue" or "carpenter s glue" are available under a number of different trade names. AppHcations are found mosdy in the area of adhesion to paper and wood (see Vinyl polymers). 

Chlorine cannot be stored economically or moved long distances. International movements of bulk chlorine are more or less limited to movements between Canada and the United States. In 1987, chlorine moved in the form of derivatives was 3.3 million metric tons or approximately 10% of total consumption (3). Exports of ethylene dichloride, vinyl chloride monomer, poly(vinyl chloride), propylene oxide, and chlorinated solvents comprise the majority of world chlorine movement. Countries or areas with a chlorine surplus exported in the form of derivatives include Western Europe, Bra2il, USA, Saudi Arabia, and Canada. Countries with a chlorine deficit are Taiwan, Korea, Indonesia, Vene2uela, South Africa, Thailand and Japan (3). 

Suspension polymerization of VDE in water are batch processes in autoclaves designed to limit scale formation (91). Most systems operate from 30 to 100°C and are initiated with monomer-soluble organic free-radical initiators such as diisopropyl peroxydicarbonate (92—96), tert-huty peroxypivalate (97), or / fZ-amyl peroxypivalate (98). Usually water-soluble polymers, eg, cellulose derivatives or poly(vinyl alcohol), are used as suspending agents to reduce coalescence of polymer particles. Organic solvents that may act as a reaction accelerator or chain-transfer agent are often employed. The reactor product is a slurry of suspended polymer particles, usually spheres of 30—100 pm in diameter they are separated from the water phase thoroughly washed and dried. Size and internal stmcture of beads, ie, porosity, and dispersant residues affect how the resin performs in appHcations. 

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