4 2001 8 ATA PL YMERIA SIIA o 4 Aug, 2001 3 1 2 2 2 1 33 ( 1 200237) ( 2 200433),, TEMP,,,,, [12,13 ], (1) [14 ], (ATRP) [3 ],2 TEMP [4 ],,,,, ( 2) ATRP TEMP(St2TEMP) TEMP(MMA2 [57 ], PSt2b2PE2b2PMMA, TEMP) (St) (MMA) ATRP PSt2b2 ATRP, PTHF [8,9 ], oca [10 ], St2TEMP MMA2TEMP ATRP PSt2b2PMMA, St MMA ATRP, Hawker [11 ] TEMP ATRP TEMP ATRP TEMP EPBr + nmma+ H 2 H 3 H 3 H 3 ul/ bpy 60 EP ( H 2 ) n (H 2 ) xl H 3 H 3 mst 120 EP ( H 2 ) n (H 2 ) xl H 3 H 3 1 EP Scheme 1 EP (H 2 H ) m 2 3 2000208212,2000210215 ; 33 459 1995-2005 Tsinghua Tongfang ptical Disc o, Ltd All rights reserved
460 2001 H 2 H 3 MMA2TEMP H 2 H H 2 Scheme 2 1 St2TEMP 111 ; ( ) ( 1 :1) ( ),50 [14 ] 2,2,6,62 115 242 212 ( HTEMP),BASF (SE) Waters 150, ( bpy) (, ), 2 ( EP2Br) Bruker 500 2 ( 12PEBr) 2,, TMS ( EIBBr) Aldrich (onv) 112 2,2,6,62 242 2, 12 ( St2TEMP) 60 ml 50 %ah,, 211 ATRP 70 ml,2 h 011 mol St2TEMP MMA2TEMP HTEMP, 24 h 200 ml, (2),, 200 ml, (2) TEMP St MMA ATRP, 3470 cm - 1 HTEMP,, 1604 cm - 1,() TEMP, ( mπz = 288) 1 74162 %, H 9101 %, 4189 %, 5 molπl), 0, 1024 h,, TEMP 3470 cm - 1 HTEMP,1730 cm - 1 ( mπz = 240) 65104 %, H 9120 %, 5192 %, 19184 %, 13 H 22 3 114 ATRP 2 3,, 3,,,, 2 1, ATRP, 11148 %, 18 H 26 2 (R2X) TEMP 1, 113 2,2, 6, 62 242 212, ( MMA2TEMP) TEMP 1,ATRP 015 mol 100 ml 015 mol HTEMP ( 1995-2005 Tsinghua Tongfang ptical Disc o, Ltd All rights reserved
4 : 461 Table 1 Synthesis of the macroinitiator via ATRP b Initiation system M 1 M 2 R2XΠM 2 Solvent a T ( ) T (h) Polymerization EP2BrΠuBrΠbpy = 1 3 St MMA2TEMP 1 3 Xyl 80 42 o 12PEBrΠuBrΠbpy = 1 3 St MMA2TEMP 1 112 Xyl 130 24 o EP2BrΠulΠbpy = 1 3 MMA MMA2TEMP 1 112 Ace 80 11 o EP2BrΠulΠbpy = 1 3 MMA St2TEMP 1 112 Ace 60 24 o EP2BrΠulΠuΠbpy = 2 1 4 St St2TEMP 2 1 Xyl 120 20 Yes a Ace : acetonitrile ; Xyl : xylene ; b [MMA] = [ St ] = 613 molπl, [ EP2Br ] = 0118 molπl 212 St2TEMP MMA2TEMP ATRP EP2BrΠuBrΠSt2TEMPΠSt,, 1 2 1, 2,,,, ( M n( GP) ) ( M n(th) ) : M n(th) = { ( [M 1 ] + [M 2 ])Π ( [ I]2[M 2 ]) } MW 1 onv,[m 1 ]St MMA,[M 2 ]St2 TEMP MMA2TEMP,[ I],MW 1 M 1,onv, 13 M 2 M 2 M 2,, [15 Matyjaszewski ] ATRP, (PS) [16 ] (PMMA), 12 PEBrΠulΠSt2TEMPΠSt 3 M 2, ( <,, ( M w ΠM n < 115), Π Fig 1 Time versus ln[m] 0 Π[M] at 100 for copolymerization of St and St2TEMP [M] 0 and [M] are the overall monomer concentration at times 0 and t,respectively Experimental conditions : [ St ] = 7124 molπl, [ EPBr ]Π[ ubr ]Π [ u]π[ bpy]π[ St2TEMP] = 4Π2Π2Π8Π3,[ St2TEMP] = 01282 molπl, xylene as solvent Fig 2 Dependence of molecular weight ( M n, ), M n(th) ( solid line) and polydispersity ( M w ΠM n, ) on monomer conversion for the copolymerization of St and St2TEMP Experimental conditions are as same as those listed in Fig 1 60 %), TEMP 100 213 St2TEMP MMA2, StΠSt2TEMP, TEMP ATRP 6 40, MMA St2TEMP 4 5,EP2BrΠ ATRP, 80 St MMA2TEMP, 1995-2005 Tsinghua Tongfang ptical Disc o, Ltd All rights reserved
462 2001, ; (2), TEMP, Fig 3 Dependence of molecular weight ( M n, ), M n(th) (solid line) and polydispersity ( M w ΠM n, ) on monomer conversion for copolymerization of St and St2TEMP at 100 Experimental conditions : [ St ] = 817 molπl, [ 12PEBr ]Π [ ul ]Π [ bpy ]Π[ St2TEMP ] = 2Π2Π6Π1, [ St2TEMP ] = 01113 molπl, xylene as solvent Fig 6 Dependence of molecular weight ( M n, ), M n(th) (solid line) and polydispersity ( M w ΠM n, ) on monomer conversion for copolymerization of MMA and St2TEMP at 40 Experimental conditions : [MMA] = 2186 molπl,[ St2TEMP] = 01118 molπl,[ EP2Br ]Π[ u]π[ ul ]Π[ bpy]π[ St2TEMP] = 3Π115Π115Π6Π2,acetonitrile as solvent Fig 4 Time versus ln[m] 0 Π[M] at 80 for copolymerization of St and MMA2TEMP Experimental conditions :[ St ] = 1018 molπl, [MMA2TEMP] = 0117 molπl, [ EP2Br ]Π[ u ]Π[ ul ]Π[ bpy ]Π[ MMA2Tempo ] = 2Π1Π1Π4Π 1,xylene as solvent Fig 7 Dependence of molecular weight ( M n, ), M n(th) ( solid line) and polydispersity ( M w ΠM n, ) on the monomer conversion for copolymerization of MMA and MMA2TEMP at 60 Experimental conditions : [ MMA ] = 417 molπl, [ MMA2TEMP ] = 01118 molπl,[ EP2Br ]Π[ u ]Π[ ul ]Π[ bpy ]Π[ MMA2TEMP ] = 3Π 115Π3Π9Π2,acetonitrile as solvent Fig 5 Dependence of molecular weight ( M n, ), M n(th) (solid line) and polydispersity ( M w ΠM n, ) on the monomer conversion for copolymerization of St and MMA2TEMP Experimental conditions are as same as those listed in Fig 4 214 8 MMAΠSt2TEMP StΠMMA2TEMP 1 H2MR 8 (a), = 316 PMMA, = 710 St2TEMP, MMAΠSt2TEMP ( M n,mr ),GP,, M w ΠM n, 118210 7 8 (b), = 710 60 MMA MMA2TEMP PS, = 316, 2 H 2 H 3 114,MMA, St2TEMP MMA2TEMP, 2 (1) St2TEMP 2, MMAΠSt2TEMP,, 60, 1995-2005 Tsinghua Tongfang ptical Disc o, Ltd All rights reserved
4 : 463 ( M w ΠM n = 114), ;, TEMP,, 315 Fig 8 1 H2MR spectra for P (MMA2co2( St2TEMP) ) and P ( St2 co2(mma2temp) ) a) P (MMA2co2( St2TEMP) ) synthesized at 60, [ MMA ] = 1018 molπl,[ EPBr ] = 0117 molπl, [ EPBr ]Π[ u ]Π[ ul ]Π[ bpy ]Π[ St2 TEMP] = 2Π1Π1Π4Π1 b) P ( St2co2( MMA2TEMP ) ) synthesized at 80, [ St ] = 1018 molπl,[ EPBr ] = 0117 molπl, [ EPBr ]Π[ u]π[ ul ]Π[ bpy]π [MMA2TEMP] = 2Π1Π1Π4Π1 Fig 9 GP trace of macroinitiator (a) and P(MMA2b2St) (b) a) Gained from the experiments, EP2BrΠulΠbpy = 1 1 2,MMAΠ Ace = 5Π5 mlπml,60,polymerized 10 h first,then added HTEMP (HTEMPΠEP2Br = 112 1) for 30 min b) Gained from the experiments of macroinitiatorπst = 1 8 ( gπml ) 120,7 h Table 2 Some physical parameters for different copolymers synthesized by ATRP Initiators (R X) M 1 M 2 R XΠM 2 Temperature ( ) M w ΠM n Average graft site number a EPBr MMA St2TEMP 2 :1 60 1140 0191 EPBr MMA MMA2TEMP 3 :2 60 1138 EPBr St MMA2TEMP 2 :1 80 1145 0185 EPBr St St2TEMP 2 :1 100 1148 0192 EPBr MMA St2TEMP 4 :3 60 1154 3171 EIBBr St MMA2TEMP 3 :2 80 1149 1196 a Average graft site number = M n,gp ΠM n,mr 1, ATRP TEMP 1, MMA ATRP (, 10 h), ( EP2Br) 112 (St HTEMP, MMA) TEMP ( St2TEMP MMA2, GP TEMP) (St 10400, 1123 St2TEMP, ) ATRP (R X),120, GP,, 91900, ;, 1186,GP 9, (3) 1995-2005 Tsinghua Tongfang ptical Disc o, Ltd All rights reserved
464 2001 Matyjaszewski [15 ], TEMP, R X TEMP, ATRP (4) R X + [L 2 u(i) ] + [L 2 u( ) X] + + R u() H 2 [L 2 u( ) X] + + H 2 R Scheme 3 R X + [L 2 u(i) ] + [L 2 u( ) X] + + R St H 2 R R ( H 2 H) n ( H 2 H ) m X H 2 Scheme 4 R, 0,1,2,31 ) 2 n + 1Π TEMP, ATRP n 1 H2MR TEMP n + 1Πn ( n = REFEREES 1 tsut T,Matsunaga T,Doi T,Matsumoto A Eur Polym J,1995,31 :6778 2 John,hong Y K,France E,Julia K,Justine J Macromolecules,1998,31 :55595562 3 Wang J S,Matyjaszewski KJ Am hem Soc,1995,117 :56145615 4 Georges M K,Veregin R P,Kazmuier P M Macromolecules,1993,26 :29872988 5 Liu Bing( ),Liu Feng( ),Luo ing( ),Ying ShengKang( ),Liu Qing( ) hemical Journal of hinese University( ),2000,21(3) :484 487 6 Liu B,Liu F,Luo and Ying S K hinese J Polym Sci,2000,18(1) :3944 7 Liu F,Luo,Liu B,Ying S K,Liu Q Polym Prepr,1999,40(2) :10321033 1995-2005 Tsinghua Tongfang ptical Disc o, Ltd All rights reserved
4 : 465 8 Liu Yanfei ( ),Wan Xiaolong( ),Ying Shengkang( ) hina Synthetic Rubber and Industry( ),1998,21 (5) : 305 9 Liu Yanfei ( ),Wan Xiaolong( ),Ying Shengkang( ) hina Synthetic Rubber and Industry( ),1998,21 (5) : 306 10 oca S,Matyjaszewski K Macromolecules,1997,30 :29082910 11 Hawker J,Barclay G G,Grubbs R B,Frecher J M J Polym Prepr,1996,37(2) : 515516 12 Liu Bing( ),Hua Fengjun( ),Yang Yuliang( ),He Jupo ( ),Hu hunpu( ) hina Synthetic Rubber and Industry ( ),1999,22(5) :373 13 Hua Fengjun( ),Yang Yuliang( ),He Jupo ( ),Liu Bing( ),Hu hunpu( ) hina Synthetic Rubber and Industry ( ),2000,23(1) :49 14 Keller R,Wycoff H D Inorg Synth,1946,2 :12 15 Matyjaszewski K,Woodworth B E,Zhang X,Gaynor S G,Metzner Z Macromolecules,1998,31 :59555957 16 Matyjaszewski K,Shipp D A,Wang J L,Grimaud T,Patten T E Macromolecules,1998,31 :68406863 STUDIES THE ATM TRASFER RADIAL PLYMERIZATI F VIYL MMER AD VIYL MMER TAIIG ITRXIDE GRUP LIU Bing 1,HUA Fengjun 2,YAG Yuliang 2,HE Junpo 2, HU hunpu 1 ( 1 Laboratory of Living Polymerization, East hina University of Science and Technology, Shanghai 200237) ( 2 Molecular Engineering pen Laboratory, Fudan University, Shanghai 200433) Abstract A new kind of macroinitiator for nitroxide2mediated polymerization was synthesized via the atom transfer radical copolymerization of styrene ( St) or methyl methacrylate (MMA) with vinyl monomer containing nitroxide group In order to gain the macroinitiator having n side nitroxide groups,the molar ratio of free radical initiator to the monomer containing nitroxide group should be at ( n + 1)Πn in the ATRP system The optimum conditions of atom transfer radical copolymerization between the St or MMA and vinyl monomer containing nitroxide group were studied in detail and the polymerization mechanism was discussed The structure of the macroinitiator was also characterized by means of 1 H2MR Key words Macroinitiator, itroxide2mediated polymerization, Atom transfer radical polymerization, Styrene, Methyl methacrylate 1995-2005 Tsinghua Tongfang ptical Disc o, Ltd All rights reserved