Monomer reacting

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. 

The order of reactivities could be also reversed by a change of solvent. For example, in THF styrene is more reactive than butadiene towards salts of polystyryl anions, whereas in hydrocarbon solvents butadiene is more reactive than styrene towards lithium polystyrene. This reversal of reactivities presumably is caused by a change in the mechanism of propagation. The monomers react directly with carbanions in THF, but become coordinated to Li+ in hydrocarbon solvents. 

Thermal Effects in Addition Polymerizations. Table 13.2 shows the heats of reaction (per mole of monomer reacted) and nominal values of the adiabatic temperature rise for complete polymerization. The point made by Table 13.2 is clear even though the calculated values for T dia should not be taken literally for the vinyl addition polymers. All of these pol5Tners have ceiling temperatures where polymerization stops. Some, like polyvinyl chloride, will dramatically decompose, but most will approach equilibrium between monomer and low-molecular-weight polymer. A controlled polymerization yielding high-molecular-weight pol)mier requires substantial removal of heat or operation at low conversions. Both approaches are used industrially. 

In a batch reactor, the relative monomer concentrations will change with time because the two monomers react at different rates. For polymerizations with a short chain life, the change in monomer concentration results in a copolymer composition distribution where polymer molecules formed early in the batch will have a different composition from molecules formed late in the batch. For living polymers, the drift in monomer composition causes a corresponding change down the growing chain. This phenomenon can be used advantageously to produce tapered block copolymers. 

Figure 10. Amount of each monomer reacted to polymer (S=M= 20 A=60 gr) 0 A, 0 S, A=H (Reproduced with permission from Ref. a. Copyright 1968 J. Wiley, Inc. ).

Mixtures of two or more monomers can polymerize to form copolymers. Many copolymers have been developed to combine the best features of each monomer. For example, poly(vinyl chloride) (called a homopolymer because it is made from a single monomers) is brittle. By copolymerizing vinyl chloride with vinyl acetate, a copolymer is obtained that is flexible. Arrangement of the monomer units in a copolymer depends on the rates at which the monomers react with each other. Graft copolymers are formed when a monomer is initiated by free radical sites created on an already-formed polymer chain. 

In interfacial polymerization, monomers react at the interface of two immiscible liquid phases to produce a film that encapsulates the dispersed phase. The process involves an initial emulsification step in which an aqueous phase, containing a reactive monomer and a core material, is dispersed in a nonaqueous continuous phase. This is then followed by the addition of a second monomer to the continuous phase. Monomers in the two phases then diffuse and polymerize at the interface to form a thin film. The degree of polymerization depends on the concentration of monomers, the temperature of the system, and the composition of the liquid phases. 

Atactic poly(methyl methacrylate/methacrylic acid), the copolymer of methyl methacrylate (MMA) and methacrylic acid (MAA), was synthesized "directly" as a prepolymer to be esterified with bis(tri-n-butyltin) oxide (TBTO). Two formulations of poly (MMA/MAA) were synthesized, a 1 1 and a 2 1 MMA and MAA copolymer whose syntheses differ only in the proportion of monomer reacted. 

Polymers are substances whose molecules are very large, formed by the combination of many small and simpler molecules usually referred to as monomers. The chemical reaction by which single and relatively small monomers react with each other to form polymers is known as polymerization (Young and Lovell 1991). Polymers may be of natural origin or, since the twentieth century, synthesized by humans. Natural polymers, usually referred to as biopolymers, are made by living organisms. Common examples of biopolymers are cellulose, a carbohydrate made only by plants (see Textbox 53) collagen, a protein made solely by animals (see Textbox 61), and the nucleic acid DNA, which is made by both plants and animals (see Textbox 64). 

Chain gro tvth polymerization begins when a reactive species and a monomer react to form an active site. There are four principal mechanisms of chain growth polymerization free radical, anionic, cationic, and coordination polymerization. The names of the first three refer to the chemical nature of the active group at the growing end of the monomer. The last type, coordination polymerization, encompasses reactions in which polymers are manufactured in the presence of a catalyst. Coordination polymerization may occur via a free radical, anionic, or cationic reaction. The catalyst acts to increase the speed of the reaction and to provide improved control of the process. 

The type of copolymer formed during step growth polymerization depends on the reactivity of the functional groups and the time of introduction of the comonomer. A random copolymer forms when equal concentrations of equally reactive monomers polymerize. The composition of the copolymer, then, will be the same as the composition of the reactants prior to polymerization. When the reactivities of the monomers-differ, the more highly reactive monomer reacts first, creating a block consisting predominandy of one monomer in the chain the lower reactivity monomer is added later. This assumes that there is no chain transfer and no monofunctional monomer present. If either of these conditions were to exist,... 

In gas phase reactors, the monomer is introduced to the bottom of reactor where it percolates up through a fluidized bed of polymer granules and inert-media supported catalyst. A fraction of the monomer reacts to form more polymer granules, the remaining monomer being drawn from the top of the reactor, cooled, and recycled. Polymer granules are continuously wthdrawn from the bottom of the fluidized bed and the catalyst is replenished. 

Reciprocal array of repeat units (this occurs when two or more monomers react together to form a complex, which is then polymerised)... 

Transformations through 1,2-addition to a formal PN double bond within the delocalized rc-electron system have been reported for the benzo-l,3,2-diazaphospholes 5 which are readily produced by thermally induced depolymerization of tetramers 6 [13] (Scheme 2). The monomers react further with mono- or difunctional acyl chlorides to give 2-chloro-l,3,2-diazaphospholenes with exocyclic amide functionalities at one nitrogen atom [34], Similar reactions of 6 with methyl triflate were found to proceed even at room temperature to give l-methyl-3-alkyl-benzo-l,3,2-diazaphospholenium triflates [35, 36], The reported butyl halide elimination from NHP precursor 13 to generate 1,3,2-diazaphosphole 14 upon heating to 250°C and the subsequent amine addition to furnish 15 (Scheme 5) illustrates another example of the reversibility of addition-elimination reactions [37],... 

It is suggested that the carbonium ion which starts the polymerization may be formed by either of two essentially different reactions, depending on the nature of the catalyst, co-catalyst and monomer. In one class of reactions the monomer reacts with a catalyst/co-catalyst complex, in the other the co-catalyst reacts with a monomer/catalyst complex. In both cases a carbonium ion and a complex anion are formed. 

The fundamental problem, why such a complexation can occur instead of the monomer reacting with the cation when it meets it in solution, is merely reformulated here in terms of potential energy minima, but not addressed clearly. The solution of that mystery did not come to this author until he started grappling with the problems presented by the polymerisations initiated by ionising radiations (Section 4.9). 

Kinetic chain length is defined as the average number of monomers reacting with a given active centre from initiation to termination and is given by... 

By numerically fitting the decay curves of [Ti(III)] with the simulation program Gepasi [52], it was established that the dimer opens the epoxide with a rate constant of k = 1.4 M 1 s, whereas the monomer reacts more slowly (k = 0.5 M 1 s 1). At the usual initial Cp2TiCl2 concentration of 10 mM, this means that 84% of 25 molecules are opened by the dimer. 

Polymers result from polymerization—the chemical combination of a large number of molecules of a certain type, called monomers. Monomers can be bifunctional (capable of joining up with two other monomers) and tri- or polyfunctional (each may join up with three or more monomers). When bifunctional monomers react with each other, you get linear thermoplastic... 

In some cases, the monomers react with themselves to form homopolymers ... 

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