ATRP 2- - PD-A - - (C-A) (P ATRP PD-A C-A M w/m n <1.4 PR-MA 50 ATRP MMA St ATRP EBP CuBr/PMDETA 20- - -1,4- -3-20- - -1,4- -3- -2- PD-Br 2- ES-Br ATRP w/m n 1.2 MMA ATRP M w/m n = 1.3-1.5 1 NMR DSC Poly(DMAEMA)[(dimethylamino) ethyl methacrylate, Poly(DMAEMA)] ATRP PR-MA Poly(PR-MA)-b-Poly(DMAEMA) Endo N -
1(4-vinylbenzoic acid 2-methylsulfanyl-4,5 nium-4-ylmethyl ester trifluoromethanesulfonate 1) M n > 10 4, M w /M n < 1.18 Lee [349] ( R )-(-)-1-(1-2- [( R)-(-)-1-(1-Naphthyl)ethyl(2-methacryloyloxyethyl)urea, NEMU] u ATRPs Kallitsis ATRP rod-coil Fukuda MAIpGlc ATRP. Kaga Ts R)-2- -2 - ( -1,1 - ATRP, cotton -rac-2,4- - ATRP addleton ATRP 20- - -1, 4--3- (PD) - C PR C-A PR-MA PD ES ATRP PD-Br ES-Br PD-A C-A PR-MA ATRP 2- EBP CuBr/PMDETA PD-Br ES-Br ATRP MMA St ATRP PD PR C C-A PD-A PR-MA PD-Br ES-Br EBP 1
3 C 3 C C 3 Br 20-(hydroxymethyl)-pregna-1,4-dien-3-one (PD) 3 C 20- (hydroxymethyl)-pregna-1, 4-dien-3-one acrylate (PD-A) C 3 C C 3 C 3 20- (hydroxymethyl)-pregna-1, 4-dien-3-one 2- bromopropionate (PD-Br) C 3 Br ethyl 2-bromopropionate (EBP) C 3 C C 3 C 3 2 C C 3 C pregnenolone (PR) pregnenolone methacrylate (PR-MA) 3 C C 3 3 C C 3 C 3 3 C 3 C C 3 C 3 C 3 β-cholestanol (C) β-cholestanol acrylate (C-A) Br C 3 Estrone (ES) estrone-2-bromopropionate (ES-Br) Figure 1. Chemical structures of PD, PD-Br, PD-A, PR, PR-MA, C, C-A, Estrone, ES-Br and EBP
1 PD-A PR-MA C-A ATRP 2 EBP/CuBr/PMDETA PD-A, PR-MA C-A PD-A C-A PR-MA 60 3 GPC M n,th = ([Monomer] /[Initiator]) Conversion M w monomer GPC PMMA Ln([M] 0 /[M]) 2.8 2.6 2.4 2.2 1.8 1.6 1.4 1.2 0.8 0.6 0.4 0.2 0.0-0.2 PR-MA C-A PD-A 0 20 40 60 80 100 120 Time (h) 100 90 80 70 60 50 40 30 20 10 0 Conversion % Figure 2. First-order kinetic plots and dependence of conversion on time for the ATRP of PD-A, PR-MA and C-A in the presence of EBP/CuBr/PMDETA in toluene at 80 o C. Solid plots represent ln([m] 0 /[M]) and open represent conversion. [Monomer] 0 :[EBP] 0 :[CuBr] 0 :[PMDETA] 0 = 50:1:1:3
M n 24000 22000 20000 18000 16000 14000 12000 10000 8000 6000 4000 2000 M n GPC,PR-MA M n GPC,C-A M n GPC,PD-A M n th,pd-a M n th,pr-ma M n th,c-a 0 0 20 40 60 80 100 Conversion % Figure 3. Dependence of M n on monomer conversion for the ATRP of PD-A, PR-MA and C-A in the presence of EBP/CuBr/PMDETA in toluene at 80 o C. [Monomer] 0 :[EBP] 0 :[CuBr] 0 :[PMDETA] 0 = 50:1:1:3 2.4 M w /M n 2.2 1.8 1.6 PR-MA C-A PD-A 1.4 1.2 0 20 40 60 80 100 Conversion % Figure 4. Dependence of M w /M n on conversion of PD-A, PR-MA and C-A. Experimental conditions are same as Figure 2. MALLS GPC 1 MALLS M n.gpc, M n.malls M n.th
4 1.5 PD-A C-A 60 M w /M n 1.3 EBP ATRP PR-MA Table 1. Comparison of molecular weight Entry M n.gpc M n.malls M n. th Polymer a 9300 13320 11930 a The polymer was obtained from the ATRP of PD-A in the presence of EBP/CuBr/PMDETA with conversion of 61.5%. M n.gpc and M n.malls were the number average molecular weight deduced from the result of GPC equipped with refractive index detector and with DAWN ES laser photometer operating at 690 nm, Wyatt Technology, respectively. M n. th was the theoretical number average molecular weight calculated from conversion and initial concentration of initiator. 2 MMA St PD-Br ES-Br ATRP PD-Br ES-Br ATRP MMA St 5 6 5 PD-Br MMA St ln([m] 0 /[M]) MMA St MMA PD-Br St 6 ES-Br MMA St PD-Br ES-Br MMA 7 8 7 8 PD-Br ES-Br MMA St MMA PD-Br ES-Br ATRP MMA M w/m n < 1.3 MMA
M w /M n = 1.4-1.5 ln([m] 0 /[M]) ln([m] 0 /[M]) 3.5 3.0 2.5 1.5 0.5 0.0 3.5 3.0 2.5 1.5 0.5 0.0 MMA 0 10 20 30 40 50 60 St Time (min) 0 5 10 15 20 25 30 Time (h) Figure 5 First-order kinetic plots for the ATRP of MMA and St in the presence of PD-Br/CuBr/PMDETA in bulk at 80 o C. [Monomer] 0 :[PD-Br] 0 :[CuBr] 0 :[PMDETA] 0 = 200:1:1:3 ln([m] 0 /[M]) ln([m] 0 /[M]) 1.8 1.6 1.4 1.2 0.8 0.6 0.4 0.2 0.0 1.8 1.6 1.4 1.2 0.8 0.6 0.4 0.2 0.0 MMA 0 10 20 30 40 50 60 70 80 90 St Time (min) 0 5 10 15 20 25 30 35 Time (h) Figure 6 First-order kinetic plots for the ATRP of MMA and St in the presence of ES-Br/CuBr/PMDETA in bulk at 80 o C. [Monomer] 0 :[ES-Br] 0 :[CuBr] 0 :[PMDETA] 0 = 200:1:1:3
M n M n 35000 MMA 30000 25000 20000 15000 10000 5000 20000 St Conversion (%) 16000 open M w /M n...m n.th 12000 8000 4000 open M w /M n M n th 0 0 20 40 60 80 100 1.8 1.6 1.4 1.2 1.8 1.6 1.4 1.2 Mw /M n Mw /M n 0 0 20 40 60 80 Conversion (%) Figure 7 Dependence of M n and M w /M n on monomer conversion for the ATRP of MMA and St in the presence of PD-Br/CuBr/PMDETA in bulk at 80 o C. [Monomer] 0 :[PD-Br] 0 :[CuBr] 0 :[PMDETA] 0 = 200:1:1:3 M n M n 28000 24000 20000 16000 12000 8000 4000 0 20000 16000 12000 8000 4000 0 MMA open M w /M n M (n,th) 0 10 20 30 40 50 60 70 80 St open M w /M n M (n,th) Conversion (%) 0 10 20 30 40 50 60 70 80 Conversion (%) 1.8 1.6 1.4 1.2 1.8 1.6 1.4 1.2 Mw /M n Mw /M n Figure 8. Dependence of M n and M w /M n on monomer conversion for the ATRP of MMA and St in the presence of ES-Br/CuBr/PMDETA in bulk at 80 o C. [Monomer] 0 :[ES-Br] 0 :[CuBr] 0 :[PMDETA] 0 = 200:1:1:3 M n, th = ([Monomer] 0 /[initiator] 0 ) M w Conversion + M w(initiator)
3 1 NMR 3.1 Poly(PD-A) PD PS 1 NMR 9 PD-A(a) Poly(PD-A)(b) 1 NMR 3.66 ppm 4.02 ppm (a in Figure 9(b)) -C 2-6.07, 6.24 7.02 ppm 9(b) b, c d 9(a) b 5.84 6.42 ppm 9(a) C 2 =C- 9 b Figure 9. 1 NMR spectra of (a) PD-A and (b) Poly(PD-A) in CDCl 3. Polymer sample: M n.gpc = 9300, M w /M n = 1.27
Figure 10. 1 NMR spectrum of PS end-capped with PD unit in CDCl 3 Polymer sample: M n.gpc = 2060, M w /M n = 1.11 PD-Br ATRP PD 10 PD 1 NMR 10 3.6 3.9 ppm ( 10 a) ( -C 2 -) 6.07, 6.24 7.02 ppm 10 b c d 4.20-4.25 ppm 10 e ph-()c(br)- 6.4-7.4 ppm 10 f M n.th = 2020 6.4-7.4 ppm 10 f PD (3.6 3.9 ppm 10 a) GPC (M n.gpc = 2060) 3.2 PR-MA MMA 1 NMR 11 PR-MA MMA 1 NMR 11(a) 11(b) 11(a) 5.39 6.08 ppm 7.11(b) PR-MA 7.11 b 3.60 ppm PMMA PR-MA MMA
Figure 11 1 NMR spectra of (a) PR-MA and (b) Poly(PR-MA- co - MMA) in CDCl 3. Experimental conditions: m (PR-MA) /m (MMA) = 4/1(g/g), [EBP] 0 :[CuBr] 0 :[PMDETA] 0 = 1:1:3, V toluene = 1 ml, 80 o C. Polymer sample: M n.gpc = 12100, M w /M n = 1.47 4 T g Autopol 20 o C Specific rotation SR, 2 3 12 2 PD-A PR-MA C-A SR P-1 P-4 Poly PD-A P-5 P-8 Poly PR-MA P-9 P-12 Poly C-A 2 P-1 P-4 SR 21 o PD +30.2 o PD-A (+23.8 o ) SR SR Poly PD-A 3970 (M w /M n = 9) 10900 (M w /M n =1.38) Poly PD-A SR Poly PD-A SR P-5 P-8 Poly PR-MA SR P-9 P-12 Poly C-A SR 5250 +17.00 o 13600 19.80 o C-A
Poly C-A Poly PR-MA Poly PD-A,, Poly PD-A Poly PR-MA Poly C-A g) 2 Poly PD-A T g 108 o C 3970 10900 T g 104.3 o C 112.4 o C Poly PR-MA Poly C-A T g Poly PD-A 100.2 110 o C 3 12 PD-Br ES-Br MMA St ATRP 3 PD-Br MMA St P-19 SR (PMMA +1 o PS +2 o ) PD 12 ES-Br 3600 SR 10.6 o 15900 SR 2.4 o 5 PR-MA MMA Sawamoto Matyjaszewski ATRP 4 PR-MA MMA Poly PR-MA-co-MMA 1.5 11 1 NMR PR-MA I MMA I 11 b b I 11 b PMMA d 1 4 PR-MA MMA
n PR-MA n MMA = I I 3 1 4 MMA SR PMMA Poly PR-MA SR PR-MA MMA 4.0 m PR-MA /m MMA 4.0 SR= +24.80 o PR-MA SR = +22.60 o 12 10 8 [α ] D 6 4 2 0 2000 4000 6000 8000 10000 12000 14000 16000 M n GPC Figure 12 The dependence of [α] D 20 on molecular weights of polymers using ES-Br as an initiator for ATRP of St in the presence of CuBr/PMDETA. Table 2. Dependence of Specific Rotation and Glass Transition Temperature on M n s of poly(pd-a), poly(pr-ma) and poly(c-a)
No. Conversion. M n. GPC (%) (M w /M n ) deg ( o C ) PD - - +30.20 - PD-A - - +23.80 - P-1 14.9 3970 (9) +21.31 104.3 P-2 29.9 5100 (1.14) +21.60 105.8 P-3 45.9 6700 (1.23) +21.39 106.1 P-4 73.4 10900 (1.38) +21.84 112.4 PN - - +21.80 - PR-MA - - +22.80 - P-5 38.2 8700 (1.44) +22.60 106.1 P-6 47.2 9100 (1.43) +22.60 107.8 P-7 72.6 11200 (1.52) +22.60 103.7 P-8 78.5 11500 (1.55) +22.60 102.8 C-A +17.00 P- 9 21.8 5250 (1.29) +17.00 109.7 P-10 28.4 6100 (1.31) +18.20 109.9 P-11 79.9 11900 (1.34) +19.40 107.6 P-12 92.3 13600(1.43) +19.80 108.7 The polymers (P-1~P-12) were obtained from the ATRPs of PD-A, PR-MA and C-A, respectively, in the presence of EBP/CuBr/PMDETA in toluene at 80 o C. [Monomer] 0 :[EBP] 0 :[CuBr] 0 :[PMDETA] 0 = 50:1:1:3. [α] D 20 Table 3. Dependence of Specific Rotation on M n s of PMMA and PS prepared using PD-Br as an initiator No. Feed ratio Conversion. M n. GPC 20 [α] D (%) (M w /M n ) (deg) PD-Br - - - +24.40 P-13 200:1:1:3 18.3 14300 (1.48) + 0 P-14 200:1:1:3 77.7 28900 (1.48) + 0.80 P-15 200:1:1:3 87.1 30300 (1.47) + 0 P-16 200:1:1:3 30.0 7300 (1.16) + 2.20 P-17 200:1:1:3 52.1 11400 (1.17) + 0 P-18 200:1:1:3 71.2 14600 (1.25) + 1.80 P-19 200:1:1:3 80.0 16100 (1.25) + 1.80 20 The [α] D values were measured on an Autopol in CCl 3 at 20 o C, = 589 nm. The polymers were obtained from the ATRPs of MMA (P-13~P-15) and St (P-16~P-19) in the presence of PD-Br /CuBr/PMDETA. [Monomer] 0 :[PD-Br] 0 :[CuBr] 0 :[PMDETA] 0 = 200:1:1:3 Table 4. Atom Transfer Radical Random Copolymerization of PR-MA and MMA in the presence of EBP/CuBr/PMDETA in toluene at 80 o C. T g
f F 20 Time [α] Conv. % M n.gpc M w /M D n (min) (deg) 0.25 0.35 40 28.8 12900 1.37 +8.00 1.36 40 39.8 12600 1.43 +17.60 4.0 10.0 40 46.4 12100 1.47 +24.80 f is feeding weight ratio of PR-MA to MMA; F is the molar ratio of PR-MA to MMA in copolymers obtained from ATRP of PR-MA and MMA in the presence of EBP/CuBr/PMDETA (1:1:3 ), which is calculated by 1 NMR. 6 Poly DMAEMA -b- poly PR-MA Poly PR-MA Poly DMAEMA (p-tscl) CuCl/PMDETA 42.2 M n = 19300 (M w /M n = 1.27) Poly(DMAEMA) ATRP CuBr/PMDETA TF PR-MA ATRP Poly(DMAEMA)-b-Poly(PR-MA) M n 45300 M w /M n = 2.26 13 GPC GPC M w /M n DMF (TEM ) Poly(DMAEMA)-b-Poly(PR-MA) 14 Poly PR-MA Poly(DMAEMA)
Minutes Figure 13 GPC traces of polymers (a) Macroinitiator, poly(dmaema) (b) block polymer, poly(dmaema)-b-poly(pr-ma). Block polymer: M n = 45300, M w /M n = 2.26; Macroinitiator: poly(dmaema) M n = 19300, M w /M n = 1.27, synthesized from ATRP of DMAEMA initiated by CuCl/PMDETA/p-TsCl Figure 14 TEM micrograph of poly(dmaema)-b-poly(pr-ma) micelles and deposited on copper grid. M n = 45300, M w /M n = 2.26 poly(dmaema) block was 19300, M w /M n = 1.27, synthesized from ATRP of DMAEMA initiated by CuCl/PMDETA/p-TsCl
PD-A C-A PR-MA ATRP PD-Br ES-Br ATRP M w /M n <1.3 PS Poly PD-A Poly PR-MA Poly C-A 23 18 o