,2 TEMPO ACTA POL YMERICA SINICA (ATRP) [3 ] ATRP. St2TEMPO MMA2TEMPO (MMA) ATRP TEMPO

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1 ATA PL YMERIA SIIA o 4 Aug, ( ) ( ),, 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 , ; Tsinghua Tongfang ptical Disc o, Ltd All rights reserved

2 H 2 H 3 MMA2TEMP H 2 H H 2 Scheme 2 1 St2TEMP 111 ; ( ) ( 1 :1) ( ),50 [14 ] 2,2,6, ( HTEMP),BASF (SE) Waters 150, ( bpy) (, ), 2 ( EP2Br) Bruker ( 12PEBr) 2,, TMS ( EIBBr) Aldrich (onv) 112 2,2,6, , 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) %, H 9101 %, 4189 %, 5 molπl), 0, 1024 h,, TEMP 3470 cm - 1 HTEMP,1730 cm - 1 ( mπz = 240) %, H 9120 %, 5192 %, %, 13 H ATRP 2 3,, 3,,,, 2 1, ATRP, %, 18 H 26 2 (R2X) TEMP 1, 113 2,2, 6, , ( MMA2TEMP) TEMP 1,ATRP 015 mol 100 ml 015 mol HTEMP ( Tsinghua Tongfang ptical Disc o, Ltd All rights reserved

3 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 o 12PEBrΠuBrΠbpy = 1 3 St MMA2TEMP Xyl o EP2BrΠulΠbpy = 1 3 MMA MMA2TEMP Ace o EP2BrΠulΠbpy = 1 3 MMA St2TEMP Ace o EP2BrΠulΠuΠbpy = St St2TEMP 2 1 Xyl 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] = 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 St2TEMP MMA2, StΠSt2TEMP, TEMP ATRP 6 40, MMA St2TEMP 4 5,EP2BrΠ ATRP, 80 St MMA2TEMP, Tsinghua Tongfang ptical Disc o, Ltd All rights reserved

4 , ; (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 ] = 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] = 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 ] = 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 MMAΠSt2TEMP StΠMMA2TEMP 1 H2MR 8 (a), = 316 PMMA, = 710 St2TEMP, MMAΠSt2TEMP ( M n,mr ),GP,, M w ΠM n, (b), = MMA MMA2TEMP PS, = 316, 2 H 2 H 3 114,MMA, St2TEMP MMA2TEMP, 2 (1) St2TEMP 2, MMAΠSt2TEMP,, 60, Tsinghua Tongfang ptical Disc o, Ltd All rights reserved

5 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 : EPBr MMA MMA2TEMP 3 : EPBr St MMA2TEMP 2 : EPBr St St2TEMP 2 : EPBr MMA St2TEMP 4 : EIBBr St MMA2TEMP 3 : 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) Tsinghua Tongfang ptical Disc o, Ltd All rights reserved

6 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 : John,hong Y K,France E,Julia K,Justine J Macromolecules,1998,31 : Wang J S,Matyjaszewski KJ Am hem Soc,1995,117 : Georges M K,Veregin R P,Kazmuier P M Macromolecules,1993,26 : Liu Bing( ),Liu Feng( ),Luo ing( ),Ying ShengKang( ),Liu Qing( ) hemical Journal of hinese University( ),2000,21(3) : Liu B,Liu F,Luo and Ying S K hinese J Polym Sci,2000,18(1) : Liu F,Luo,Liu B,Ying S K,Liu Q Polym Prepr,1999,40(2) : Tsinghua Tongfang ptical Disc o, Ltd All rights reserved

7 4 : Liu Yanfei ( ),Wan Xiaolong( ),Ying Shengkang( ) hina Synthetic Rubber and Industry( ),1998,21 (5) : Liu Yanfei ( ),Wan Xiaolong( ),Ying Shengkang( ) hina Synthetic Rubber and Industry( ),1998,21 (5) : oca S,Matyjaszewski K Macromolecules,1997,30 : Hawker J,Barclay G G,Grubbs R B,Frecher J M J Polym Prepr,1996,37(2) : Liu Bing( ),Hua Fengjun( ),Yang Yuliang( ),He Jupo ( ),Hu hunpu( ) hina Synthetic Rubber and Industry ( ),1999,22(5) : 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 : Matyjaszewski K,Shipp D A,Wang J L,Grimaud T,Patten T E Macromolecules,1998,31 : 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 ) ( 2 Molecular Engineering pen Laboratory, Fudan University, Shanghai ) 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 Tsinghua Tongfang ptical Disc o, Ltd All rights reserved