MULTICHAIN POLYMERIZATION in .NET

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MULTICHAIN POLYMERIZATION
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Aramid polymers are much more expensive than the aliphatic polyamides. The use of aramid polymers is limited to those applications that justify the high cost. The present U.S. market is about 20 million pounds per year. The applications are those where one needs very high ame resistance (clothing for re ghters and welders, welder s protective shield, upholstery and drapes), heat resistance (ironing board covers, insulation lm for electrical motors and transformers, aerospace and military), dimensional stability ( re hose, V- and conveyor belts), or strength and modulus (circuit boards, bulletproof vests, ber optic and power lines, ship mooring ropes, automobile tire cord, puncture-resistant bicycle tires).
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Historical Aspects
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Wallace Carothers and coworkers at DuPont synthesized aliphatic polyesters in the 1930s [Furukawa, 1998; Hounshell and Smith, 1988]. These had melting points below 100 C, which made them unsuitable for rber use. Carothers then turned successfully to polyamides, based on the theoretical consideration that amides melt higher than esters. Polyamides were the rst synthetic bers to be produced commercially. The polyester and polyamide research at DuPont had a major impact on all of polymer science. Carothers laid the foundation for much of our understanding of how to synthesize polymeric materials. Out of that work came other discoveries in the late 1930s, including neoprene, an elastomer produced from chloroprene, and Te on, produced from tetra uoroethylene. The initial commercial application for nylon 6/6 was women s hosiery, but this was short-lived with the intrusion of World War II. The entire nylon 6/6 production was allocated to the war effort in applications for parachutes, tire cord, sewing thread, and rope. The civilian applications for nylon products burst forth and expanded rapidly after the war. Carother s work not only secured the future of the DuPont chemical empire but launched the synthetic ber industry and changed the agricultural patterns of the Southern cotton states. Subsequent to the success of nylon, workers in the United Kingdom in the early 1950s achieved success in producing a polyester ber by using terephthalate as the acid component. Cotton, no longer King of Fibers, accounts for less than 25% of the U.S. ber market. Nylon, PET, and rayon (regenerated cellulose) account for the remainder.
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2-9 MULTICHAIN POLYMERIZATION 2-9a Branching
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The discussions until this point have been concerned with the polymerization of bifunctional monomers to form linear polymers. When one or more monomers with more than two functional groups per molecule are present the resulting polymer will be branched instead of linear. With certain monomers crosslinking will also take place with the formation of network structures in which a branch or branches from one polymer molecule become attached to other molecules. The structures of linear, branched, and crosslinked polymers are compared in Fig. 1-2. Consider the polymerization of an A reactant in the presence of a small amount of a B monomer Af containing f functional groups per molecule. The value of f is termed the functionality of the monomer. The product of this polymerization will be a branched polymer in which f chains are attached to a central branch point (i.e., an Af species). For the speci c case A j A of f 3, polymerization of A in the presence of B leads to the structure XVI. A A
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STEP POLYMERIZATION
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careful consideration of this structure shows that there can be only one Af reactant molecule incorporated into each polymer molecule. Further, crosslinked species will not be formed. Reactions between two polymer molecules of the type described above cannot occur since all growing branches possess A functional groups at their ends. Branch chains from one molecule cannot react with those from another. (This would not be true if A groups were capable of reacting with each other. However, that is not the usual situation.) Polymerizations with extensive branching are considered elsewhere. Sections 2-10 and 2-16 discuss branching with and without crosslinking, respectively.
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