Small Concentrations of Initiators

To derive kinetic relationships for polymerizations at low yields ( 5%), it is assumed that  

Monomer is consumed only in the propagation reaction and not in other reactions, such as the start reaction or termination by monomer. For these conditions to remain fulfilled to 1 % within experimental error, the number-average degree of polymerization X must be at least 100. The rate of the propagation reaction is then approximately equal to that of the overall reaction  

The principle of equal chemical reactivity should be valid (see Section 16.4.3), so that the rate constant for the propagation reaction does not depend on the molecular weight. 

The concentrations of polymer free radicals P and initiator free radicals RJ should be constant, i.e., the steady-state principle is valid  

Initiator free radicals are formed by the decomposition reaction and consumed in the start reaction  

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The weight loss corresponding to NH3 and HCN is very large in some cases (up to 65%) and this is, as discussed by Grassie and McGuchan [139], not consistent with the concept of a small concentration of initiating sites and... 

Polyester resins can also be rapidly formed by the reaction of propylene oxide (5) with phthaUc and maleic anhydride. The reaction is initiated with a small fraction of glycol initiator containing a basic catalyst such as lithium carbonate. Molecular weight development is controlled by the concentration of initiator, and the highly exothermic reaction proceeds without the evolution of any condensate water. Although this technique provides many process benefits, the low extent of maleate isomerization achieved during the rapid formation of the polymer limits the reactivity and ultimate performance of these resins. 

Although laboratory tests (NACE TMO 169-76, and Reference 313) are obviously of value in selecting materials they cannot simulate conditions that occur in practice, and although an initial sorting may be made on the basis of these tests ultimate selection must be based on tests in the plant. This is particularly important where the process streams may contain small concentrations of unknown corrosive species whose influence cannot be assessed by laboratory trials. Testing is also important for monitoring various phenomena such as embrittlement, hydrogen uptake, corrosion rates, etc. which are considered in Section 19.3. 

A very small concentration of hydrogen and hydroxide ions, originating from the small but finite ionisation of water, will be initially present. HA is a weak acid, i.e. it is dissociated only to a small degree the concentration of A- ions which can exist in equilibrium with H+ ions is accordingly small. In order to... 

As for equilibrium values of as and P they are mainly dependent on relations between such parameters of the systems as initial electric conductivity of adsorbent, concentration of chemisorbed particles, reciprocal position of the energy levels of absorbate and adsorbent. Thus, during acceptor adsorption in case of small concentration of adsorption particles one can use (1.82) and (1.84) to arrive to expressions for equilibrium values of ohmic electric conductivity and the tangent of inclination angle of VAC ... 

Classically the base catalyst, eOEt, is introduced by adding just over one mole of sodium (as wire, or in other finely divided form) plus just a little EtOH to generate an initial small concentration of Na eOEt. Further EtOH is generated in step (1), which yields further Na eOEt with sodium, and the concentration of eOEt is thereby maintained. A whole mole is required as it is essential for the / -keto ester (114) to be converted (step 3) into its anion (115)—MeCOCH2-COzEt is more acidic than EtOH (cf. p.272)—if the overall succession of equilibria is to be displaced to the right. This is necessary because the carbanion-formation equilibrium—step (1)—lies even further over to the left than that with, for example, CH3CHO this reflects the less effective stabilisation through delocalisation in the ester carbanion (111) than in that from the aldehyde (116) ... 

Ionic Polymerization. Ionic polymerizations, especially cationic polymerizations, are not as well understood as radical polymerizations because of experimental difficulties involved in their study. The nature of the reaction media is not always clear since heterogeneous initiators are often involved. Further, it is much more difficult to obtain reproducible data because ionic polymerizations proceed at very fast rates and are highly sensitive to small concentrations of impurities and adventitious materials. Butyl rubber, a polymer of isobutene and isoprene, is produced commercially by cationic polymerization. Anionic polymerization is used for various polymerizations of 1,3-butadiene and isoprene. 

A variety of initiators have been used for cationic polymerization. The most useful type of initiation involves the use of a Lewis acid in combination with small concentrations of water or some other proton source. The two components of the initiating system form a catalyst-cocatalyst complex which donates a proton to monomer... 

Like all controlled radical polymerization processes, ATRP relies on a rapid equilibration between a very small concentration of active radical sites and a much larger concentration of dormant species, in order to reduce the potential for bimolecular termination (Scheme 3). The radicals are generated via a reversible process catalyzed by a transition metal complex with a suitable redox manifold. An organic initiator (many initiators have been used but halides are the most common), homolytically transfers its halogen atom to the metal center, thereby raising its oxidation state. The radical species thus formed may then undergo addition to one or more vinyl monomer units before the halide is transferred back from the metal. The reader is directed to several comprehensive reviews of this field for more detailed information. 

The decomposition of initiator can be followed by usual analytical methods and k can be determined. The efficiency factor/can be obtained by comparing the amount of initiator [I] decomposed with the number of polymer chain formed. The rate of polymerization can be determined by monitoring the change in a physical or chemical property of the system. Generally, dilatometry technique is used for determination of the rate of polymerization. Let the extent of polymerization be small and concentration of initiator be constant. Let r0, rt and r be the readings on dilatometer initially, at time t and at the completion of reaction, respectively. If reaction is first order in [M],... 

Compare Eq. 3-229 with 3-224. The decay in monomer concentration depends on the orders of both initiator and activator initial concentrations with no dependence on deactivator concentration and varies with t2/3 under non-steady-state conditions. For steady-state conditions, there are first-order dependencies on initiator and activator and inverse first-order dependence on deactivator and the time dependence is linear. Note that Eq. 3-229 describes the non-steady-state polymerization rate in terms of initial concentrations of initiator and activator. Equation 3-224 describes the steady-state polymerization rate in terms of concentrations at any point in the reaction as long as only short reaction intervals are considered so that concentration changes are small. 

If a small concentration of A is generated in a great excess of B, then even if (17) is allowed to go to completion, the concentration of B will remain essentially constant at its initial concentration [B] . Integrating (S) and treating [B]n as constant, one obtains... 

Oxygen has two possible interactions during the polymerization process [94], and these reactions are illustrated in Fig. 2. The first of these is a quenching of the excited triplet state of the initiator. When this quenching occurs the initiator will absorb the light and move to its excited state, but it will not form the radical or radicals that initiate the polymerization. A reduction in the quantum yield of the photoinitiator will be observed. The second interaction is the reaction with carbon based polymerizing radicals to form less reactive peroxy radicals. The rate constant for the formation of peroxy radicals has been found to be of the order of 109 1/mol-s [94], Peroxy radicals are known to have rate constants for reaction with methyl methacrylate of 0.241/mol-s [100], while polymer radicals react with monomeric methyl methacrylate with a rate constant of 5151/mol-s [100], This difference implies that peroxy radicals are nearly 2000 time less reactive. Obviously, this indicates that even a small concentration of oxygen in the system can severely reduce the polymerization rate. 

The polymerization is carried out at 78°C in THF. In order to modify the reactivity of the terminal carbanion, a small excess, with respect to the initial concentration of initiator, either of a methylstyrene or diphenylethylene, is added to the living polymer. 

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