Free radical polymerization ceiling temperature

Free radical polymerization Ceiling temperature Comonomer Post-s)mthesis adducts... 

Rhombic sulfur is a brittle, crystalline solid at room temperature. Heating to 113 °C causes it to melt to a reddish-yellow liquid of relatively low viscosity. Above approximately 160 °C, the viscosity increases dramatically because of the free-radical polymerization of the cyclic molecules into long, linear chains.6,8 14 30 47-51 At this point, a degree of polymerization of approximately 105 is obtained. If the temperature is increased to above approximately 175 °C, depolymerization occurs, as evidenced by a decreasing viscosity. A similar type of depolymerization occurs with the polysiloxanes discussed in Chapter 4. In thermodynamic terms, the negative -TAS term overcomes the positive AH term for chain depolymerization. (The temperature at which the two terms are just equal to one another is called the ceiling temperature for the polymerization.)... 

A major limitation of a-methylstyrene in free-radical polymerizations is its very low ceiling temperature of 61 °C.347 As a result, AMS is utilized commercially only in radical copolymerization. Nonetheless, it is among the most active CCT monomers with Cc = 9 x 105 at 50 °C for 9a as CCT catalyst.348 This value is relatively unchanged at 40 °C. This high value reflects the low kp = 1.7 M 1 s 1 so that kc = 5 x 105 M-1 s 1. 

Poly(2-methyl-1-pentene sulfone) (PMPS) is an alternating copolymer of 2-methyl-l-pentene (2MP) and sulfur dioxide. The formation of PMPS occurs only by a free radical polymerization mechanism and is complicated to a degree by ceiling temperature considerations. For all exothermic addition polymerization reactions there is a critical temperature called the ceiling temperature (Tc) above which no reaction occurs. The precise Tc depends upon the monomer concentration according to the expression (i)... 

When depropagation takes place at an elevated temperature, at a rate that is equal to the propagation in a free-radical polymerization, then the temperature of the reaction is a ceiling temperature (see Chap. 3). Termination can take place by disproportionation. Secmidary reactions, however, may occur in the degradation process depending upon the chemical structure of the polymer. Such side reactions can, for instance, be successive eliminations of hydrochloric acid, as in poly(vinyl chrolide), or acetic acid as in poly(vinyl acetate). 

Thus the values shown in Table 1.8 are for standard conditions and represent just one of a series of ceiling temperatures for various monomer concentrations above which polymer formation is not favoured. Thus, in a bulk polymerization reaction the ceiling temperature may change with conversion in such a way that complete conversion is not achieved. For example, if methyl methacrylate is polymerized at 110°C the value of [M]c calculated from the above equation is 0.139M and this will be the monomer concentration in equilibrium with the polymer. The polymer, when removed from the monomer, will have the expected ceiling temperature as given in Table 1.8 and will depolymerize only if there is a source of free radicals to initiate the depolymerization (Section 1.4.1)... 

It is impossible to synthesize a polymer from its monomers above T. If the polymer is synthesized below its ceiling temperature and then brought to a temperature above its in the presence of traces of the polymerization catalyst, for instance, a free radical, it will spontaneously depolymerize. It is this... 

The ceiling temperature constraint in the homopolymerization of alphamethyl styrene (AMS) can be circumvented by copolymerization with acrylonitrile (AN) to prepare multicomponent random microstructures that offer higher heat resistance than SAN. The feasibility of a thermal initiation of free radical chain polymerization is evaluated by an experimental study of the terpolymerization kinetics of AMS-AN-Sty. Process considerations such as polyrates, molecular weight of polymer formed, sensitivity of molecular weight, molecular weight distribution, and kinetics to temperature were measured. 

Most monomers are above their free-radical ceiling temperature and only a single monomer unit is often added onto the polymer backbone. This is notably the case with maleic anhydride, acrylic acid, and methyl methacrylate. Styrene is an exception and one graft polymerize long polystyrene chains onto polyolefins [223]. 

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