M(MMA)=100.12 [MMA] = 8.48 mol/L M(styrene)=104.15 [styrene] = 0.82 mol/L [RN] = 0.0273 mol/L [N] = 0.00274 mol/L # reaction coefficients kd0 = 3.4e-2 kc0 = 5.0e+6 kt0 = 2.0e+9 kp01 = 1.9e+4 kp02 = 2.56e+4 kcR1 = 1.1e+6 kcR2 = 4.6e+6 kdR1 = 1.17 kdR2 = 3.4e-3 ktR1R1 = 2.0e+9 ktR1R2 = 2.0e+9 ktR2R2 = 2.0e+9 kpR11 = 1.64e+3 kpR12 = 3.33e+3 kpR21 = 6.65e+2 kpR22 = 3.25e+2 kp111 = 1.64e+3 kp222 = 9.0e+2 kp112 = 3.33e+3 kp121 = 6.65e+2 kp122 = 3.25e+2 kp211 = 9.86e+2 kp212 = 2.0e+3 kp221 = 1.84e+3 kc1 = 1.4e+4 kc2 = 4.5e+5 kd11 = 1.17 kd12 = 3.4e-3 kd21 = 6.9e-2 kd22 = 2.5e-4 ktd11 = 2.8e+7 ktd12 = 1.8e+7 ktd22 = 1.9e+6 ktc11 = 6.5e+6 ktc12 = 1.8e+7 ktc22 = 3.3e+7 kbHtr = 1.69e+3 temperature = 90 �C # reactions # Homolytic dissociation of the alkoxyamine RN --kd0--> R + N # Recombination of the alkoxyamine R + N --kc0--> RN # Homotermination of the 2-(hydroxycarbonyl)prop-2-yl radical R + R --kt0--> RR # Addition of the 2-(hydroxycarbonyl)prop-2-yl radical onto M1 R + MMA --kp01--> RM1(1) # Addition of the 2-(hydroxycarbonyl)prop-2-yl radical onto M2 R + styrene --kp02--> RM2(1) # Reversible combination of the R-M1# radical adduct with SG1 RM1(n) + N --kcR1--> RM1N(n) # Reversible combination of the R-M2# radical adduct with SG1 RM2(n) + N --kcR2--> RM2N(n) # Homolytic dissociation of the SG1-terminated R-M1N alkoxyamines RM1N(n) --kdR1--> RM1(n) + N # Homolytic dissociation of the SG1-terminated R-M2N alkoxyamines RM2N(n) --kdR2--> RM2(n) + N # Homotermination between R-M1# radical adducts RM1(n) + RM1(m) --ktR1R1--> RM1M1R(n+m) # Termination between R-M1# and R-M2# radical adducts RM1(n) + RM2(m) --ktR1R2--> RM1M2R(n+m) # Homotermination between R-M2# radical adducts RM2(n) + RM2(m) --ktR2R2--> RM2M2R(n+m) # Addition of the R-M1# radical adduct onto M1 RM1(n) + MMA --kpR11--> PM1M1(n+1) # Addition of the R-M1# radical adduct onto M2 RM1(n) + styrene --kpR12--> PM1M2(n+1) # Addition of the R-M2# radical adduct onto M1 RM2(n) + MMA --kpR21--> PM2M1(n+1) # Addition of the R-M2# radical adduct onto M2 RM2(n) + styrene --kpR22--> PM2M2(n+1) # Additionb of the PM1M1# propagating macroradical onto M1 PM1M1(n) + MMA --kp111--> PM1M1(n+1) # Additionb of the PM2M2# propagating macroradical onto M2 PM2M2(n) + styrene --kp222--> PM2M2(n+1) # Additionb of the PM1M1# propagating macroradical onto M2 PM1M1(n) + styrene --kp112--> PM1M2(n+1) # Additionb of the PM1M2# propagating macroradical onto M1 PM1M2(n) + MMA --kp121--> PM2M1(n+1) # Additionb of the PM1M2# propagating macroradical onto M2 PM1M2(n) + styrene --kp122--> PM2M2(n+1) # Additionb of the PM2M1# propagating macroradical onto M1 PM2M1(n) + MMA --kp211--> PM1M1(n+1) # Additionb of the PM2M1# propagating macroradical onto M2 PM2M1(n) + styrene --kp212--> PM1M2(n+1) # Additionb of the PM2M2# propagating macroradical onto M1 PM2M2(n) + MMA --kp221--> PM2M1(n+1) # Reversible combination of the P-M1-M1# propagating macroradical with SG1 PM1M1(n) + N --kc1--> PM1M1N(n) # Reversible combination of the P-M2-M1# propagating macroradical with SG1 PM2M1(n) + N --kc1--> PM2M1N(n) # Reversible combination of the P-M2-M2# propagating macroradical with SG1 PM2M2(n) + N --kc2--> PM2M2N(n) # Reversible combination of the P-M1-M2# propagating macroradical with SG1 PM1M2(n) + N --kc2--> PM1M2N(n) # Homolytic dissociation of the SG1-terminated P-M1-M1N alkoxyamine PM1M1N(n) --kd11--> PM1M1(n) + N # Homolytic dissociation of the SG1-terminated P-M1-M2N alkoxyamine PM1M2N(n) --kd12--> PM1M2(n) + N # Homolytic dissociation of the SG1-terminated P-M2-M1N alkoxyamine PM2M1N(n) --kd21--> PM2M1(n) + N # Homolytic dissociation of the SG1-terminated P-M2-M2N alkoxyamine PM2M2N(n) --kd22--> PM2M2(n) + N # Irreversible termination between a P-M1-M1# and a P-M1-M1# propagating macroradical by disproportionation PM1M1(n) + PM1M1(m) --ktd11--> D(n) + D(m,TDB) # Irreversible termination between a P-M1-M1# and a P-M2-M1# propagating macroradical by disproportionation PM1M1(n) + PM2M1(m) --ktd11--> D(n) + D(m,TDB) # Irreversible termination between a P-M1-M1# and a P-M2-M1# propagating macroradical by disproportionation PM2M1(n) + PM2M1(m) --ktd11--> D(n) + D(m,TDB) # Irreversible termination between a P-M1-M1# and a P-M2-M2# propagating macroradical by disproportionation PM1M1(n) + PM2M2(m) --ktd12--> D(n) + D(m,TDB) # Irreversible termination between a P-M1-M1# and a P-M1-M2# propagating macroradical by disproportionation PM1M1(n) + PM1M2(m) --ktd12--> D(n) + D(m,TDB) # Irreversible termination between a P-M2-M1# and a P-M1-M2# propagating macroradical by disproportionation PM2M1(n) + PM1M2(m) --ktd12--> D(n) + D(m,TDB) # Irreversible termination between a P-M2-M2# and a P-M2-M2# propagating macroradical by disproportionation PM2M2(n) + PM2M2(m) --ktd22--> D(n) + D(m,TDB) # Irreversible termination between a P-M2-M2# and a P-M1-M2# propagating macroradical by disproportionation PM2M2(n) + PM1M2(m) --ktd22--> D(n) + D(m,TDB) # Irreversible termination between a P-M1-M2# and a P-M1-M2# propagating macroradical by disproportionation PM1M2(n) + PM1M2(m) --ktd22--> D(n) + D(m,TDB) # Irreversible termination between a P-M1-M1# and a P-M1-M1# propagating macroradical by combination PM1M1(n) + PM1M1(m) --ktc11--> D(n+m) # Irreversible termination between a P-M1-M1# and a P-M2-M1# propagating macroradical by combination PM1M1(n) + PM2M1(m) --ktc11--> D(n+m) # Irreversible termination between a P-M1-M1# and a P-M2-M1# propagating macroradical by combination PM2M1(n) + PM2M1(m) --ktc11--> D(n+m) # Irreversible termination between a P-M1-M1# and a P-M2-M2# propagating macroradical by combination PM1M1(n) + PM2M2(m) --ktc12--> D(n+m) # Irreversible termination between a P-M1-M1# and a P-M1-M2# propagating macroradical by combination PM1M1(n) + PM1M2(m) --ktc12--> D(n+m) # Irreversible termination between a P-M2-M1# and a P-M1-M2# propagating macroradical by combination PM2M1(n) + PM1M2(m) --ktc12--> D(n+m) # Irreversible termination between a P-M2-M2# and a P-M2-M2# propagating macroradical by combination PM2M2(n) + PM2M2(m) --ktc22--> D(n+m) # Irreversible termination between a P-M2-M2# and a P-M1-M2# propagating macroradical by combination PM2M2(n) + PM1M2(m) --ktc22--> D(n+m) # Irreversible termination between a P-M1-M2# and a P-M1-M2# propagating macroradical by combination PM1M2(n) + PM1M2(m) --ktc22--> D(n+m) # �-hydrogen transfer from a P-M1-M1# propagating macroradicals to the nitroxide SG1 PM1M1(n) + N --kbHtr--> DbHtr(n) # �-hydrogen transfer from a P-M1-M1# propagating macroradicals to the nitroxide SG1 PM2M1(n) + N --kbHtr--> DbHtr(n)