Kinetics polymer degradation

Polymer chemists use DSC extensively to study percent crystallinity, crystallization rate, polymerization reaction kinetics, polymer degradation, and the effect of composition on the glass transition temperature, heat capacity determinations, and characterization of polymer blends. Materials scientists, physical chemists, and analytical chemists use DSC to study corrosion, oxidation, reduction, phase changes, catalysts, surface reactions, chemical adsorption and desorption (chemisorption), physical adsorption and desorption (physisorp-tion), fundamental physical properties such as enthalpy, boiling point, and equdibrium vapor pressure. DSC instruments permit the purge gas to be changed automatically, so sample interactions with reactive gas atmospheres can be studied. 

Lazzari S, Codari R, Storti G, Morbidelli M, Moscatelli D. Modeling the pH-dependent PLA oligomer degradation kinetics. Polym Degrad Stab 2014 110 80-90. 

X. Colin, B. Fayolle, L. Audouin, J. Verdu. About a quasi-universal character of unstabilised polyethylene thermal oxidation kinetics. Polymer Degradation and Stability 80(1), 67-74, (2003). 

There have been many studies on the thermal and thermo-oxidative degradation of PMMA.23 24 It is well established that the polymer formed by radical polymerization can be substantially less stable than predicted by consideration of the idealized structure and that the kinetics of polymer degradation are dependent on the conditions used for its preparation. There is still some controversy surrounding the details of thermal degradation mechanisms and, in particular, the initiation of degradation.31... 

Well before the advent of modern analytical instruments, it was demonstrated by chemical techniques that shear-induced polymer degradation occurred by homoly-tic bond scission. The presence of free radicals was detected photometrically after chemical reaction with a strong UV-absorbing radical scavenger like DPPH, or by analysis of the stable products formed from subsequent reactions of the generated radicals. The apparition of time-resolved ESR spectroscopy in the 1950s permitted identification of the structure of the macroradicals and elucidation of the kinetics and mechanisms of its formation and decay [15]. 

As previously stated, GPC is the method of choice for studying polymer degradation kinetics. The GPC trace, as given by the detector output, does not provide the true MWD due to various diffusion broadening processes inside the different parts of the equipment. The first step is to correct for instrument broadening if a precise evaluation of MWD is desired. Even with the best columns available, this correction may change the MWD significantly as can be visualized... 

Starting with the results of GPC analysis, two approaches have been successfully applied to the problem of polymer degradation, using either the differential or the integral expression of the kinetics equations a) in the first technique, a number of GPC traces are recorded at successive degradation times or degradation yields. Each MWD is divided in a number of... 

It is most fortunate for the development of polymer science that these imagined complications have turned out to be almost wholly illusory. As will be brought out in the course of this chapter, the influence of molecular size and complexity on chemical reactivity may be disregarded in very nearly all polymer reactions. If this were not the case, application of the principles of reaction kinetics to polymerization and polymer degradation reactions would be difficult, and might be so complicated as to be fruitless. Not only would polymer reaction kinetics... 

G.A. George, Use of chemiluminescence to study the kinetics of oxidation of solid polymers. In N. Grassie (Ed.), Developments in Polymer Degradation-3, Applied Science Publishers, London, 1981, p. 173. 

It is important to distinguish between erosion and degradation. Erosion is mass loss from a bioerodible polymer and may be a consequence of polymer dissolution or degradation of the polymer backbone, followed by dissolution of the degradation products. Degradation typically occurs by hydrolysis of the polymer backbone, the kinetics of which is a function of the polymer chemistry. Thus, erosion is the sum of several elementary processes, one of which may be polymer degradation. 

In their study of branched PSA, Maniar et al. (1990) found that the molecular architecture of branched polymers affects the release kinetics in a variety of ways. They found that the branched polymers degraded faster than linear PSA of comparable molecular weight (Maniar et al., 1990). They also noted that drug (morphine) release profiles were more characteristic of bulk erosion than surface erosion An initial lag time during which very little drug was released was associated with the time required for water to swell the polymer. This was followed by a period of relatively fast release, which tapered off as the device disintegrated. The polymer matrix lost its mechanical integrity before the release experiment was complete (Maniar et al., 1990). Despite the increase... 

This reaction is very exothermic (A// —180 to —200kJ mol-1) and, therefore, seems to be very probable from the thermochemical point of estimation. The pre-exponential factor is expected to be low due to the concentration of the energy on three bonds at the moment of TS formation (see Chapter 3). To demonstrate that this reaction is responsible for the oxidative destruction of polymers, PP and PE were oxidized in chlorobenzene with an initiator and analyzed for the rates of oxidation, destruction (viscosimetrically), and double bond formation (by the reaction with ozone) [131]. It was found that (i) polymer degradation and formation of double bonds occur concurrently with oxidation (ii) the rates of all three processes are proportional to v 1/2, (iii) independent of p02, and (iv) vs = vdbf in PE and vs = 1.6vdbf in PP (vdbf is the rate of double bond formation). Thus, the rates of destruction and formation of double bonds, as well as the kinetic parameters of these reactions, are close, which corroborates with the proposed mechanism of polymer destruction. Therefore, the rate of peroxyl macromolecules degradation obeys the kinetic equation ... 

At elevated temperatures, the oxidation of PE occurs as a quasistationary process with the kinetic equilibrium between the formation and decay of hydroperoxyl groups (see Chapter 4). The ratio of the two discussed reactions of polymer degradation is ... 

VS Pudov. Kinetics and Mechanism of Solid Polymer Degradation and Stabilization, Doctoral Thesis Dissertation, Institute Chemical Physics, Moscow, 1980. 

Peng S, An Y, Chen C, Fei B, Zhuang Y, Dong L (2003) Thermal degradation kinetics of uncapped and end-capped poly(propylene carbonate). Polym Degrad Stab 80 141-147... 

Herzog K, Muller RJ, Deckwer WD (2006) Mechanism and kinetics of the enzymatic hydrolysis of polyester nanoparticles by lipases. Polym Degrad Stab 91 2486-2498... 

Grollmann U, Schnabel W (1980) On the kinetics of polymer degradation in solution, 9. Pulse radiolysis of polyethylene oxide). Makromol Chem 181 1215-1226 Hamer DH (1986) Metallothionein. In Richardson CC, Boyer PD, Dawid IB, Meister A (eds) Annual review of biochemistry. Annual Reviews, Palo Alto, pp 913-951 Held KD, Harrop HA, Michael BD (1985) Pulse radiolysis studies of the interactions of the sulfhydryl compound dithiothreitol and sugars. Radiat Res 103 171-185 Hilborn JW, PincockJA (1991) Rates of decarboxylation of acyloxy radicals formed in the photocleavage of substituted 1-naphthylmethyl alkanoates. J Am Chem Soc 113 2683-2686 Hiller K-O, Asmus K-D (1983) Formation and reduction reactions of a-amino radicals derived from methionine and its derivatives in aqueous solutions. J Phys Chem 87 3682-3688 Hiller K-O, Masloch B, Gobi M, Asmus K-D (1981) Mechanism of the OH radical induced oxidation of methionine in aqueous solution. J Am Chem Soc 103 2734-2743 Hoffman MZ, Hayon E (1972) One-electron reduction of the disulfide linkage in aqueous solution. Formation, protonation and decay kinetics of the RSSR radical. J Am Chem Soc 94 7950-7957... 

B. Interpreting the Kinetics of Polymer Degradation in the Solid State... 

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