Polymerization peroxide value

Numerous polymers autooxidize to form peroxides. These compositionally, and thus calorimetrically, ill-defined products may be considered polymeric peroxides. However, one well-defined polymeric peroxide is that of polystyrene with the repeat unit —CHa-CH(CeH5)-0-0-. Through a combination of combustion and reaction calorimetry (chain degradation to benzaldehyde and formaldehyde), a solid phase enthalpy of formation of this species was found to be 27 21 kJ mol . Much the same procedure was used to determine the enthalpy of degradation for the polyperoxide polymers of 2-vinylnaphthalene and the isomeric 1- and 2-propenylnaphthalene to form the related acylnaphthalene and formaldehyde. Numerically, the reaction enthalpy values for these last three polyperoxides were —206+4, —222 + 8 and —222 + 10 kJmol, to be compared with the aforementioned polystyrene with a value of —209 + 8 kJ mol. However, in the absence of enthalpy of formation data for the decomposition products in the naphthalene case, we hesitate to derive enthalpies of formation for these three species. ... 

Polymer immobilization. Mo-peroxide, 427 Polymerization agents, 621, 622 peroxide value, 661, 662 peroxycarboxyUc acids, 698 radical polymerization, 697, 707 styrene, 697, 720 sulfonyl peroxides, 1005 thermochemistry, 155 Polymers aging, 685 autoxidation, 623 hydroperoxide determination, 685 Poly(methacrylonitrile peroxide)... 

Fats with peroxide values of 100 (88) cause no obvious effect when fed to rats. Peroxide values of 800 will cause loss of appetite and decreasing ability to gain weight, while values of 1200 can be quite toxic. Peroxide values in excess of 100 are rarely encountered with good commercial practices (89). Heat-induced cyclization or polymerization of fats results in quite toxic compounds when tested with rats. These materials may affect membrane function (90), liver enlargement (91) and other biological systems(92). 

Inhibition of spontaneous polymerization of (meth) acrylates is necessary not only at their storage but also in the conditions of their synthesis proceeding in the presence of sulfuric acid. In this case, monomer stabilization is more urgent, since sulfuric acid not only deactivates mat r inhibitors but also is capable of intensifying polymer formation. The concentration dependence of induction periods in these conditions has a brightly expressed nonlinear character. And, unlike polymerization in bulk, decomposition of polymeric peroxides is observed at relatively low temperatures in the presence of sulfuric acid, and the values [X] of the amines studied are by ca. 10 times lower than [HQ]. ... 

Reactions (6) and (10) alternate to give polymeric peroxide. The more stable the alkyl radical formed due to addition, the faster the addition reaction. Below we present the lo values (l/(mol s)) for several monomers at 303 K. 

Because the peroxodisulfate salts are all made electrochemicaHy, the electrical energy cost is a significant part of thek manufacturing cost. The 1994 world capacity for peroxodisulfate salts was about 75,000 metric tons, valued at about 30 x 10 . The principal appHcations are in polymerization catalysis and the market broadly tracks the plastics business. The Caro s acid business is difficult to quantify because the product itself is not commercial but made on-site from purchased hydrogen peroxide. 

The activation energy for the spontaneous decomposition of benzoyl peroxide is 30 ( 1) kcal. per mole, and the same value applies also within experimental error to the azo nitrile.The apparent activation energy for the polymerization of styrene initiated by either is about 23 kcal. per mole, therefore. 

Literature data for the suspension polymerization of styrene was selected for the analysi. The data, shown in Table I, Includes conversion, number and weight average molecular weights and initiator loadings (14). The empirical models selected to describe the rate and the instantaneous properties are summarized in Table II. In every case the models were shown to be adequate within the limits of the reported experimental error. The experimental and calculated Instantaneous values are summarized in Figures (1) and (2). The rate constant for the thermal decomposition of benzoyl peroxide was taken as In kd 36.68 137.48/RT kJ/(gmol) (11). 

The Instantaneous values for the initiator efficiencies and the rate constants associated with the suspension polymerization of styrene using benzoyl peroxide have been determined from explicit equations based on the instantaneous polymer properties. The explicit equations for the rate parameters have been derived based on accepted reaction schemes and the standard kinetic assumptions (SSH and LCA). The instantaneous polymer properties have been obtained from the cummulative experimental values by proposing empirical models for the instantaneous properties and then fitting them to the cummulative experimental values. This has circumvented some of the problems associated with differenciating experimental data. The results obtained show that ... 

Some examples, such as thermal polymerization of styrene and decomposition of di-f-butyl peroxide, are given in [194], both treated as first-order reactions. The activation energy found for the decomposition of di-f-butyl peroxide agrees well with the literature value. From the pressure data, it appears that the initial pressure rise is caused by the evaporation of toluene, present as a solvent. At higher temperatures, the gases generated by decomposition are the main contributors to the pressure rise. 

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