Boreskov Institute of Catalysis of the Siberian Branch of Russian ...

PP-II-13dMdt− k*315= M⋅ M23⋅ ( k+ k164⋅ R⋅ M*3+ k+ k817⋅ M*1⋅ M4+ k12) − k⋅ M22*2⋅ M+ k*316⋅ ( M⋅ M*1*3+ M) − M*2*3+ M⋅ ( k*314+ M⋅ M*4)1−(1)dMdt− k*419dMdt− k118= M⋅ M⋅ M2= −k*44⋅(k+ k2⋅ M20⋅ R15⋅ R⋅ M**3⋅ M1+ k+ k921− k6⋅ M*1⋅ M⋅ M4*1+ k13) − k⋅ M1⋅ M22*2⋅ M− k10+ k*417⋅(M⋅ M*2⋅ M*1*3+ M⋅ M) − M1*2− k*4+ M14⋅(k*3⋅ MdM2 ****= −M2⋅(k3⋅ R + kM7⋅ M1+ k11⋅ M2+ k15⋅ M3+ k19⋅dtdM3 ****= −M3⋅(k4⋅ R + kM8⋅ M1+ k12⋅ M2+ k16⋅ M3+ k20⋅dtdM4 ****= −M4⋅(k5⋅ R + kM9⋅ M1+ k13⋅ M2+ k17⋅ M3+ k21⋅dt+ k2222⋅ M*2*3⋅ M*2*4+ k2222⋅ M*2*4⋅ M*3*422*2*422*318⋅ M+ MdP* ** ** **= k22⋅ M1⋅ M1+ k22⋅ M1⋅ M2+ k22⋅ M1⋅ M3+ k22⋅ M1⋅ Mdt+ k ⋅ M ⋅ M + k ⋅ M ⋅ M + k ⋅ M ⋅ M + k ⋅ M ⋅ M +where I – a molecule of hydroperoxide of ethylbenzene; R * – primary initiating radical; M 1 –a molecule of cis- piperylene; M 2 – a molecule of trans- piperylene; M 3 – a molecule ofdivinyl; M 4 – a molecule of vinylacetylene; M * 1, M * 2, M * 3, M * 4 – growing (increasing)radicals; P – a molecule of polymer; k 0 , k 1 – reaction rate constants of initiator consumption;k 2 , k 3 , k 4 , k 5 – reaction rate constants of initialization; k 6 , k 7 , …, k 21 – reaction rate constantsof chain growth; k 22 , k 23 , …, k 31 – reaction rate constants of chain interruption.The system (1) is the mathematical description of kinetics of copolymerization of thetranse-cis-isomers of piperylene with divinyl and vinyl acetate.It is known that while solving an inverse problem of kinetics one of the challenges is thedefinition of the parametres which values can be found for the accepted kinetic scheme on thebasis of the available experimental information. As parametres of the model of kinetics ofcopolymerization constants K 2 , …, K 31 were accepted . For the quantitative assessment of thedivergence of experimental data and the results of calculations the functional of the type wasaccepted:Q =722222∑ [( IЭ− IP) + ( M1Э− M1P) + ( M2Э− M2 P) + ( M3Э− M3P) + ( M4Э− M4 P) ]i=1*3*3*4⋅ M*4*4*4)))*411)+−−295