By Lyudmila Shibryaeva, Anatoly Popov, Gennady Zaikov
The purpose of this ebook is to explain the advanced challenge about the connection among the constitution and mechanism of oxidation of heterogeneous and heterophase polymer structures. the fabric offered during this ebook matters the explicit beneficial properties of the kinetics of oxidation and people of the constitution of polymer platforms.
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Extra info for Thermal Oxidation of Polymer Blends: The Role of Structure
As it is known, if at the stage of interaction of peroxide radical with comonomer units the intra-molecular reaction prevails, then usual block hydroperoxides are formed . Under inter-molecular interaction of hydroperoxide radicals with monomer units the single hydroperoxides predominate . The ratio between contents of block and single ROOH and also the length of hydroperoxide block in copolymer depend on the structure of its macro-chain. The nature of comonomer, its content, block structure of copolymer chains influence on physical-dynamics parameters of copolymer , consequently on the mechanism of formation and properties of hydroperoxide.
In the case of phase or micro-phase separation of comonomers in copolymer when reaction abilities of comonomers are significantly differed or in the case of cell effect revealing in comonomers with various rigidity of chain the initiation of kinetic chains of oxidation of one of comonomers may significantly delay in comparison with the other one. In this case oxidation will develop locally in blocks of more active comonomer that was reported in works [138, 149151, 170]. Thus, initiation of kinetic chains of oxidation of less active in relation to oxygen comonomer is possible in reaction being the stage of continuation of kinetic chains of oxidation of more active comonomer, for example by the following reaction: (10) M1* + M2H oM1H + M2* and also: M2* + M1H oM2H + M1* (11) Initiation on the stage of kinetic chain continuation in copolymer also may occur as a result of intermolecular transfer of free valency from monomer M1 of one macromolecule to comonomer M2 of the other macromolecule.
Unfreezing of movement in strengthened trough-pass chains fixed by crystals is realized at the expense of change of rotary-isomer composition of these chains via ToGtransirions . It may occurs with the beginning of melting of the smallest solder pads and will determine relaxation at temperatures lower than Tmel by 1015qC. The most probable reason of appearance of lowtemperature shoulder on DSC curve of oxidized PP1 is coagulation of trough-pass interlamellar chains with the lowest degree of coagulation under unfreezing of their mobility at front surfaces of crystallites.