Initiation initiator decomposition

We recall some of the ideas of kinetics from the summary given in Sec. 5.2 and recognize that the rates of initiator decomposition can be developed in terms of the reactions listed in the Table 6.1. Using the change in initiator radical concentration d[I-]/dt to monitor the rates, we write the following ... 

Table 6.2 Rate Constants (at Temperature Given) and Activation Energies for Some Initiator Decomposition Reactions...

For photoinitiation there is no activation energy for the initiator decomposition hence... 

Note that the initiator decomposition makes the largest contribution to E therefore photoinitiated processes display a considerably lower temperature dependence for the rate of polymerization. 

The problems of monomer recovery, reaction medium viscosity, and control of reaction heat are effectively dealt with by the process design of Montedison Fibre (53). This process produces polymer of exceptionally high density, so although the polymer is stiU swollen with monomer, the medium viscosity remains low because the amount of monomer absorbed in the porous areas of the polymer particles is greatly reduced. The process is carried out in a CSTR with a residence time, such that the product k jd x. Q is greater than or equal to 1. is the initiator decomposition rate constant. This condition controls the autocatalytic nature of the reaction because the catalyst and residence time combination assures that the catalyst is almost totally expended in the reactor. 

More recent work reports the onset of thermal degradation at lower temperatures and provides a clearer picture of the role of oxygen (73—75). In the presence of oxygen, backbone oxidation and subsequent cleavage reactions initiate decomposition. In the absence of oxygen, dehydrofluorination eventually occurs, but at significantly higher temperatures. 

The calculated detonation velocity in room temperature acetylene at 810 kPa is 2053 m/s (61). Measured values are about 1000-2070 m/s, independent of initial pressure but generally increasing with increasing diameter (46,60—64). In a time estimated to be about 6 s (65), an accidental fire-initiated decomposition flame in acetylene at ca 200 kPa in an extensive piping system traveled successively through 1830 m of 76—203-mm pipe, 8850 m of 203-mm pipe, and 760 m of 152-mm pipe. 

Activation Parameters. Thermal processes are commonly used to break labile initiator bonds in order to form radicals. The amount of thermal energy necessary varies with the environment, but absolute temperature, T, is usually the dominant factor. The energy barrier, the minimum amount of energy that must be suppHed, is called the activation energy, E. A third important factor, known as the frequency factor, is a measure of bond motion freedom (translational, rotational, and vibrational) in the activated complex or transition state. The relationships of yi, E and T to the initiator decomposition rate (kJ) are expressed by the Arrhenius first-order rate equation (eq. 16) where R is the gas constant, and and E are known as the activation parameters. 

The activation parameters for an initiator can be deterrnined at normal atmospheric pressure by plotting In vs 1/T using initiator decomposition rates obtained in dilute solution (0.2 M or lower) at several temperatures. Rate data from dilute solutions are requited in order to avoid higher order reactions such as induced decompositions. The intercept for the resulting straight line is In and the slope of the line is —E jR therefore both and E can be calculated. 

The second generation includes latices made with functional monomers like methacrylic acid, 2-hydroxyethyl acrylate [818-61 -17, acrylamide/75 -(9ti-/7, 2-dimethylaminoethylmethacrylate [2867-47-2] and sodiumT -vinyl-benzenesulfonate [98-70-4] that create in polymeric emulsifier. The initiator decomposition products, like the sulfate groups arising from persulfate decomposition, can also act as chemically bound surfactants. These surfactants are difficult to remove from the latex particle. 

The above mechanism, together with the assumptions that initiator decomposition is rate controlling and that a steady state in chain radicals exists, results in the classical expressions (eqs. 8 and 9) for polymerization rate, and number-average degree of polymerization, in a homogeneous,... 

Polyethylene is the simplest of so-called high polymers. The reaction for low density polyethylene (LDPE) follows the classical free radical polymerization steps of initiator decomposition, initiation, propagation, and termination. The reaction is... 

The polymerization of acrylamide in aqueous solutions in the presence of alkaline agents leads to the ob-tainment of partially hydrolyzed polyacrylamide. The polymerization process under the action of free radicals R (formed on the initiator decomposition) in the presence of OH ion formed on the dissociation of an alkali addition (NaOH, KOH, LiOH), and catalyzing the hydrolysis can be described by a simplified scheme (with Me = Na, K, Li) ... 

EDTA begins to decompose at only 400 psig (441 °F, 27.5 bar, 227 °C). However, the initial decomposition products are weaker chelants, hydroxyethyliminodiacetic acid (HEIDA) and iminodiacetic acid (IDA), so chelation still takes place. (Hydrolysis of HEIDA then continues at a much slower rate to produce more IDA and ethylene glycol.) Despite this reversion problem, EDTA is effective and, in practice, is employed at up to 1,200 psig (82.7 bar) and up to 1,500 psig (103.4 bar) when employed as an overlay product. 

Rienaecker and Werner [907] suggest that Ba3(Mn04)2 is the initial decomposition product, by analogy with results for KMn04. Isothermal a—time curves for vacuum decomposition at 413—463 K were sigmoid... 

Peroxodiphosphoric acid (PDPA) may also be used to convert sulphoxides to sulphones in good yields. An initial study of this reaction80 concluded that the mechanism was a free radical process, involving the reaction of a hydroxyl radical with the sulphoxide as shown in equation (26). This was later claimed to be incorrect the reaction actually occurs by the initial decomposition of PDPA to PMPA which then reacts as described above81. 

Thermal degradation studies of EB-cured terpolymeric fluorocarbon rubber [430] by nonisothermal thermogravimetry in the absence and presence of cross-link promoter TMPTA reveal that thermal stability is improved on radiation and more so in the presence of TMPTA. Initial decomposition temperature, maximum decomposition temperature and the decomposition... 

The peroxide-initiated, free radical, dispersion polymerization of the single monomer is assumed to progress according to the simultaneous reactions of initiator decomposition, initiation, propagation and termination with appropriate reaction orders described elsewhere.(2-6)... 

In the above reactions, I signifies an initiator molecule, Rq the chain-initiating species, M a monomer molecule, R, a radical of chain length n, Pn a polymer molecule of chain length n, and f the initiator efficiency. The usual approximations for long chains and radical quasi-steady state (rate of initiation equals rate of termination) (2-6) are applied. Also applied is the assumption that the initiation step is much faster than initiator decomposition. ,1) With these assumptions, the monomer mass balance for a batch reactor is given by the following differential equation. 

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