Formation polymers

Synthetic polymers used to form fibers are often classified on the basis of their mechanism of polymerization--step growth (condensation) or chain growth (addition) polymerization. Step growth polymerization involves multifunctional monomers which undergo successive condensation with a second monomer or with itself to form a dimer, which in turn condenses with another dimer to form a tetramer, etc., usually with loss of a small molecule such as water. Chain growth involves the instantaneous growth of a long molecular chain from unsaturated monomer units, followed by initiation of a second chain, etc. The two methods are outl ined below schematically  

For this purpose, monomers show a special combination of different elements, so-called reactive groups that, instead of the metaphorically called hooks and eyes , combine with the groups of neighboring monomers by chemical reaction. Thus, polymer structures develop from straight and branched or crosslinked chains. These reactive groups will be explained in more detail when the most important adhesives are discussed. 

If only a limited number of monomers combine by chemical reaction, then one talks of prepolymers, a preliminary stage of polymers, however, still showing reactive groups. They are partly applied in mixtures with similarly structured monomers. To simplify matters, the term monomer continues to be used in this book. 

Bridging groups may join coordinated metal atoms to form dimers, trimers and so on 

If a methanol solution of sodium azide is added to a chloroform solution of cuprous chloride and triphenylphosphine, the dimer which is obtained contains a bridging azide group (8.112). 

On the other hand, sulphur reacts with the palladium azide complex to give a dimer which is linked by N atoms as indicated in (8.113). Unlike in the copper complex where all the N-N distances are equal, unequal distances in the palladium complex indicate the triple bonds as shown (8.97). Dinitrogen may act as a bridging group as in 

Magnesium does not form phosphine complexes as readily as most other metals but pincer-type ligands (8.116) are exceptions [27]. (See (8.152) below.) 

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The addition polymerization of a vinyl monomer CH2=CHX involves three distinctly different steps. First, the reactive center must be initiated by a suitable reaction to produce a free radical or an anion or cation reaction site. Next, this reactive entity adds consecutive monomer units to propagate the polymer chain. Finally, the active site is capped off, terminating the polymer formation. If one assumes that the polymer produced is truly a high molecular weight substance, the lack of uniformity at the two ends of the chain—arising in one case from the initiation, and in the other from the termination-can be neglected. Accordingly, the overall reaction can be written... 

The rate at which monomer is consumed is equal to the rate of polymer formation ... 

Smith, D. A. (Ed.), Addition Polymers Formation and Characterization, Plenum Press, New York, 1968. 

Losses by polymer formation kept the yield of acryhc acid to 60—70%. Preferably, esters were prepared dkecdy by a simultaneous dehydration—esterification process. 

Acryhc acid and esters are stabilized with minimum amounts of inhibitors consistent with stabihty and safety. The acryhc monomers must be stable and there should be no polymer formation for prolonged periods with normal storage and shipping (4,106). The monomethyl ether of hydroquinone (MEHQ) is frequentiy used as inhibitor and low inhibitor grades of the acrylate monomers are available for bulk handling. MEHQ at 10—15 ppm is generally... 

In addition to graft copolymer attached to the mbber particle surface, the formation of styrene—acrylonitrile copolymer occluded within the mbber particle may occur. The mechanism and extent of occluded polymer formation depends on the manufacturing process. The factors affecting occlusion formation in bulk (77) and emulsion processes (78) have been described. The use of block copolymers of styrene and butadiene in bulk systems can control particle size and give rise to unusual particle morphologies (eg, coil, rod, capsule, cellular) (77). 

To produce a spandex fiber by reaction spinning, a 1000—3500 molecular weight polyester or polyether glycol reacts with a diisocyanate at a molar ratio of about 1 2. The viscosity of this isocyanate-terrninated prepolymer may be adjusted by adding small amounts of an inert solvent, and then extmded into a coagulating bath that contains a diamine so that filament and polymer formation occur simultaneously. Reactions are completed as the filaments are cured and solvent evaporated on a belt dryer. After appHcation of a finish, the fibers are wound on tubes or bobbins and rewound if necessary to reduce interfiber cohesion. 

THPC—Amide Process. The THPC—amide process is the first practical process based on THPC. It consists of a combination of THPC, TMM, and urea. In this process, there is the potential of polymer formation by THPC, melamine, and urea. There may also be some limited cross-linking between cellulose and the TMM system. The formulation also includes triethanolamine [102-71-6J, an acid scavenger, which slows polymerization at room temperature. Urea and triethanolamine react with the hydrochloric acid produced in the polymerization reaction, thus preventing acid damage to the fabric. This finish with suitable add-on passes the standard vertical flame test after repeated laundering (80). 

Cuprous salts catalyze the oligomerization of acetylene to vinylacetylene and divinylacetylene (38). The former compound is the raw material for the production of chloroprene monomer and polymers derived from it. Nickel catalysts with the appropriate ligands smoothly convert acetylene to benzene (39) or 1,3,5,7-cyclooctatetraene (40—42). Polymer formation accompanies these transition-metal catalyzed syntheses. 

Polymer formation 2 RMgR + heat RMgRC=CH2Mg + alkane... 

The concept of functionaUty and its relationship to polymer formation was first advanced by Carothers (15). Flory (16) gready expanded the theoretical consideration and mathematical treatment of polycondensation systems. Thus if a dibasic acid and a diol react to form a polyester, assumiag there is no possibihty of other side reactions to compHcate the issue, only linear polymer molecules are formed. When the reactants are present ia stoichiometric amouats, the average degree of polymerization, follows the equatioa ... 

Process considerations must not only take into account characteristics of the particular alcohol or phenol to be esterified, but also the self-propagating by-product reaction, which results in polymer formation. 

Because PEA is such an important fragrance material this simple, essentially one-step process has been exhaustively studied to optimize reaction conditions and purification procedures. Because of the high reactivity of the iatermediates and the tendency toward polymer formation, critical factors such as throughput, temperature, molar ratios of reactants, addition rates, reactor materials and design, and agitation rate must be carefully balanced to provide an economical product with acceptable odor properties. 

An example of an appHcation of hydrocracking is in lubricating oils, where it is used to improve the viscosity index, color, and color stabiHty to reduce polymer formation (storage stabiHty) and to decrease the neutralization number (acidity) (61). 

Under certain conditions hydrogen cyanide can polymerize to black soHd compounds, eg, hydrogen cyanide homopolymer [26746-21-4] (1) and hydrogen cyanide tetramer [27027-02-2], C H N (2). There is usually an incubation period before rapid onset of polymer formation. Temperature has an inverse logarithmic effect on the incubation time. Acid stabilizers such as sulfuric and phosphoric acids prevent polymerization. The presence of water reduces the incubation period. 

If pure monomer is to be used ia a reactioa, it must be used iaimediately or stored at < — 20° C to preveat dimerization to any appreciable extent. Chemical inhibition does not prevent dimerization low temperature is preferred. If the monomer has to be stored for more than a few hours, it must be protected against oxygen to prevent peroxidation and polymer formation. Cyclopentadiene monomer reacts spontaneously with oxygen of the air to form brown, gummy peroxide-containing products. 

Fire and uncontroUed polymerization are a concern in the handling of chloroprene monomer. The refined monomer is ordinarily stored refrigerated under nitrogen and inhibited. This is supported by routine monitoring for polymer formation and vessel temperature. Tanks and polymerization vessels are equipped for emergency inhibitor addition. Formalized process hazard studies, which look beyond the plant fence to potential for community involvement, are routine for most chemical processes. 

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