Atom Transfer Radical Polymerization Krzysztof Matyjaszewski* and Jianhui Xia Department of Chemistry, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213 Received February 15, 2001 I. Gii thiu 2921 8. Tm tt v Outlook 2935 II. Ghi nh my mc ca Atom Chuyn E. chuyn tip-kim loi phc hp 2935 Radical trng hp 1. Nhm 6: Molypden v Chromium 2935 2923 2. Nhm 7: Rhenium 2936 A. Cc thnh phn 2923 3. Nhm 8: ruthenium v st 2936 1. Monome 2923 4. Nhm 9: Rhodium 2938 2. Khi xng nm 2924 5. Nhm 10: Niken v Palladium 2938 3. Cht xc tc 2924 6. Nhm 11: ng 2939 4. Dung mi 2924 7. Tm tt v Outlook 2940 5. Thi gian nhit v phn ng 2925 F. phi t 2941 6. Ph gia 2925 1. Nit phi t 2941 B. Hin tng tiu biu 2925 2. Photpho phi t 2941 1. ng hc 2925 3. Miscellaneous phi t 2942 2. Trng lng phn t 2926 4. Tm tt v Outlook 2942 3. Trng lng phn t phn phi 2926 G. Ph gia 2942 4. Bnh thng v ngc ATRP 2927 C cu H. Catalyst 2943 5. Th nghim ci t 2927 I. C ch 2945 6. Cht xc tc ng nht 2927 J. tng th tiu Hai 2947 7. Tm tt v Outlook 2928 III. Vt liu Made by ATRP 2949 C. monome ATRP 2928 A. Chc nng 2949 1. Styrenes 2928 1. Monomer Chc nng 2949 2. Acrylates 2929 2. Initiator Chc nng 2952 3. Methacrylates 2929 3. Chui Cui Chc nng 2955 4. Acrylonitrile 2930 4. Tm tt v Outlook 2957 5. (Ly) acrylamides 2930 B. Thnh phn 2957 6. (Ly) axit acrylic 2931 1. Copolyme Gradient / thng k 2958 7. Linh tinh monome 2931 2. Khi copolyme 2960 8. Tm tt v Outlook 2931 3. Lai v c / Hu C 2969 D. khi ATRP 2932 4. Tm tt v Outlook 2970 1. Dn xut halogen ha alkan 2932 C. Cu trc lin kt 2972 2. Benzylic Halogenua 2932 1. Ghp copolyme 2972 3. R-Haloesters 2933 2. Ghp t b mt 2977 4. R-Haloketones 2933 3. Sao Polymers 2978 5. R-Halonitriles 2934 4. Hyperbranched Polymers 2981 6. Sulfonyl Halogenua 2934 5. Tm tt v Outlook 2983 7. Bnh lun v cc Initiator IV. Kt lun 2983 C cu trong ATRP V. Xc Nhn 2985 2934 VI. Ti liu tham kho 2985 II. I. Gii thiu Tng hp cc polyme thnh phn vi nhng quy nh, kin trc, v cc chc nng t lu c quan tm rt ln trong polymer ha hc. Thng thng, k thut trng hp sng c tuyn dng polymerizations tin hnh trong trng hp khng chuyn giao khng th o ngc chui v chui termination.1-3 Phn ln cc nghin cu khoa hc v cng nghip sng trng hp tp trung vo anionic, cationic, phi hp, v vng m polymerizations. Cc pht trin trng hp cc oan kim sot / sng (CRP) cc phng php c mt mc tiu lu di trong polymer ha hc, nh mt qu trnh trit hn khoan dung ca cc nhm chc nng v cc tp cht v cng nghip hng u phng php sn xut polymers.4 Mc d tin ch cng nghip to ln ca n, CRP khng c thc hin1

cho n gn y, phn ln l do khng th trnh khi gc t do, kim sot gn khuch tn bimolecular khp ni v phn ng disproportionation. Chem. Rev. 2001, 101, 2921-2990 2921 10.1021/cr940534g CCC: $ 36,00 2001 Hip hi Ha hc Hoa K c ng trn Web 2001/09/12 Ti v ca Nguyn M vo ngy 30 thng 8 nm 2009 http://pubs.acs.org Ngy xut bn (Web): Thng Chn 12, 2001 | doi: 10.1021/cr940534g Nhng nm qua chng kin nhanh chng tng trng trong s pht trin v s hiu bit mi Methods.5 CRP, 6 Tt c nhng phng php ny c da trn thit lp mt cn bng nng ng, nhanh chng gia mt s lng pht ngy cng tng cc gc t do v mt ln a s cc loi khng hot ng. Khng hot ng dy chuyn c th c alkyl halogenua, nh trong nguyn t chuyn cn bn trng hp (ATRP) hoc thoi ha chuyn giao (DT), thioesters, nh trong phn mnh Ngoi ra o ngc chuyn chui cc qu trnh (b), alkoxyamines, trng hp trung gian nitroxide (NMP) hoc n nh gc t do trng hp (SFRP), v c kh nng ngay c cc loi hu c. Cc gc t do c th c to ra bi qu trnh t pht nhit (NMP, SFRP) thng qua mt phn ng xc tc (ATRP) hoc thun nghch thng qua qu trnh trao i thoi ha vi khng hot ng loi (DT, b). Tt c cc phng php CRP, th hin trong n 1, bao gm cc bc kch hot v v hiu ha (vi t l hng s kact v kdeact), mc d trong b v DT chng trnh c th c chnh thc n gin ch l qu trnh trao i vi cc hng s t l r rng kexch. To ra cc gc t do tuyn truyn v chm dt (Vi t l hng kp v kt), nh trong mt thng thng trng hp gc t do. V vy, mc d chm dt xy ra, trong iu kin thch hp ca n ng gp s c nh (t hn mt vi phn trm tng s dy chuyn) v nhng polymerizations trit hot ng h thng gn nh sng hoc kim sot. Nhn xt ny s tp trung vo cc nguyn tc c bn ca xc tc kim loi chuyn tip nguyn t chuyn cn bn trng hp (ATRP). Chng ti s tho lun v hin ti s hiu bit c ch ca qu trnh ny v mt s tng hp cc ng dng c kt qu trong mt lot vt liu c xc nh r. Tng quan ny bao gm cc vn hc t u ca lnh vc ny (1995) cho n khi khong cui nm 2000. Chng ti ch yu tham kho giy t xut bn trong cc tp ch peer-xem xt li, tr khi cng vic xut hin trong vn hc nonpeer-nhn xt v khng theo sau bi mt n phm y . Mt c ch chung cho ATRP th hin trong n 2 tng ng vi trng hp 2 t n 1. Cc gc t do, hoc cc loi hot ng, c to ra thng qua mt o ngc oxi ha kh qu trnh xc tc bi mt kim loi chuyn tip Krzysztof (Kris) Matyjaszewski c sinh ra trong Konstantynow, Ba Lan, vo nm 1950. ng ly bng tin s ca mnh mc vo nm 1976 ti Vin Hn lm Khoa hc Ba Lan ti Lodz, Ba Lan, lm vic trong phng th nghim ca Gio s S. Penczek. ng nhn c Bng Habilitation ca mnh vo nm 1985 t Lodz Polytechnic, Ba Lan. ng li nh mt nghin cu sinh sau tin s ti i hc Florida, lm vic vi Gio s G. B. Butler. T nm 1985, ng c ti i hc Carnegie Mellon University, ni ng phc v l Trng B phn Ha hc (1994-1998) v hin ang l JC Warner Gio s Khoa hc t nhin. ng cng l mt gio s tr ging ti B Du kh v K thut Ha hc ti i hc Pittsburgh v Ba Lan Hc vin Khoa hc Lodz, Ba Lan. ng l Gio s Thnh ging ti cc trng i hc ti Paris, Strasbourg, Bordeaux, Bayreuth, Freiburg, Ulm, v Pisa. ng l mt bin tp vin ca Tin b Khoa hc trong Polymer v phc v Ban bin tp ca tp ch polymer. Chnh li ch nghin cu ca mnh bao gm phn ng trng hp kim sot / sng vi s nhn mnh gn y ca h thng gc t do. Nm 1995, ng pht trin nguyn t chuyn cn bn trng hp (ATRP), mt trong nhng phng php thnh cng nht cho iu khin / sng trit trng hp (CRP). Trong 5 nm qua ca mnh nhm (25 nghin cu sinh sau tin s v sau i hc 23 v 26 hc sinh vin) xut bn hn 200 giy t v ATRP v CRP. ng c hn 20 bng sng ch M v quc t. Tng tc cht ch cng nghip c duy tr bi Hip hi ATRP (13 cng ty trong 1996-2000) v va c thnh lp CRP Consortium (19 cng ty giai on 2001-2005). Nghin cu ca Matyjaszewski nhm nhn c s cng nhn rng ri, nh bng chng l Carl ACS S. Marvel gii thng Sng to Polymer Ha hc (1995), Elf Ch tch Vin Hn lm Khoa hc Php (1998), Humboldt gii thng cho nh khoa hc cao cp ca M (1999), gio s quc gia Ba Lan (2000), hc bng ca ACS Phng Vt liu Polymeric K thut (2001), Gii thng ACS Pittsburgh (2001), v gii thng ACS trong Ho Polymer (2001). Jianhui Xia l mt nh khoa hc nghin cu cao cp trong cng ty R & D ti 3M Cng ty Saint Paul, MN. ng nhn c B.S. mc trong Polymer Ha hc nm 1991 ca trng i hc Khoa hc v Cng ngh ca Trung Quc lm vic vi Gio s Dezhu Ma. Sau , ng n i hc Emory ca Atlanta, GA, ni ng thu c M.S. mc trong Ha hc hu c v tng hp bt i xng t Gio s Dennis Liotta. ng ginh c bng tin s ca mnh mc trong Polymer Ha hc trong nm 1999 v kim sot / "sng" cc oan trng hp ti i hc Carnegie Mellon theo ch o ca Gio s Krzysztof Matyjaszewski. Quan tm nghin cu hin ti ca ng bao gm tng hp kim sot ca cun tiu thuyt vt liu cao phn t. n 1. Chng trnh chung ca phng php CRP 2922 Ha cht, nm 2001, Vol. 101, s 9 Matyjaszewski v Xia mTi v ca Nguyn M vo ngy 30 thng 8 nm 2009 http://pubs.acs.org Ngy xut bn (Web): Thng Chn 12, 2001 | doi: 10.1021/cr940534g phc tp (Mtn-Y/Ligand, Y c th l mt mphi t hoc counterion) m tri qua mt oneelectron qu trnh oxy ha vi tru tng ng thi ca mt (Gi) nguyn t halogen, X, t mt loi khng hot ng, R-X. Qu trnh ny xy2

ra vi mt tc lin tc ca mkch hot, kact v kdeact Chm dt hot. Polymer chui tng vic b sung cc gc trung gian monome trong mt cch tng t nh mt thng thng trng hp cc oan, vi t l khng i tuyn truyn kp. Chm dt phn ng (kt) cng xy ra ATRP, ch yu l thng qua khp ni cc oan v disproportionation; Tuy nhin, trong mt ATRP c kim sot tt, khng qu vi phn trm ca cc chui polymer tri qua chm dt. Phn ng ph khc c th b sung hn ch trng lng phn t c th t c. Thng thng, khng qu 5% ca tng s ngy cng tng cc chui polymer chm dt trong thi gian ngn, ban u, bt tnh giai on ca phn ng trng hp. Qu trnh ny to ra cc phc kim loi b oxy ha, X-Mt n +1, nh gc t do lin tc gim nng tnh ca cc gc t pht trin v do gim thiu s ng gp ca termination.7 ATRP thnh cng s c khng ch l mt ng gp nh ca chm dt dy chuyn, nhng cng tng trng thng nht ca tt c cc dy chuyn, l thc hin thng qua bt u nhanh v Chm dt hot hi phc nhanh chng. Tn trng hp nguyn t gc t do chuyn nhng (ATRP) bt ngun t cc bc chuyn giao nguyn t, m l phn ng tiu hc trng im chu trch nhim v thng nht tng trng ca cc chui polymer, trong cng mt cch m cc phn mnh Ngoi ra l bc quan trng trong qu trnh b. ATRP c ngun gc trong nguyn t chuyn Ngoi ra gc t do (ATRA), m mc tiu hnh thnh l 1:1 adducts alkyl halogenua v alkene, cng c xc tc bi kim loi chuyn tip complexes.8 ATRA l mt sa i ca phn ng Ngoi ra Kharasch, thng xy ra trong s hin din ca nh sng hoc thng thng trit initiators.9 Do s tham gia ca kim loi chuyn tip trong vic kch hot v v hiu ha bc, ha tr, Regio, v stereoselectivities trong ATRA v vic b sung Kharasch c th khc nhau. i vi V d, theo iu kin Kharasch, trong phn ng bng cht chloroform alkene s "chn" trn ton quc. H-CCl3 tri phiu nhng trong ATRA n s chn qua Cl-CHCl2 tri phiu, v s lin kt C-Cl nhanh chng kch hot bng Fe (II) hoc Cu (I) complexes.10 ATRP cng c ngun gc trong cc kim loi chuyn tip xc tc telomerization reactions.11 Nhng phn ng ny, Tuy nhin, khng tin hnh trao i hiu qu, m kt qu trong mt s tin ha phi tuyn ca cc phn t trng lng vi cc chuyn i v polyme cao polydispersities. ATRP cng c cc kt ni n kim loi chuyn tip bt u qu trnh oxi ha kh l nh c ch vi kim loi chuyn tip compounds.12-14 Hai k thut ny cho php kch hot hoc mt Chm dt hot qu trnh, tuy nhin, khng c hiu qu o ngc. ATRP c pht trin bi thit k mt cht xc tc thch hp (hp cht kim loi chuyn tip v phi t), s dng mt khi vi c cu ph hp, v iu chnh cc iu kin trng hp trng lng phn t tng tuyn tnh vi chuyn i v cc polydispersities c in hnh sng process.15-19 ny cho php mt cha tng c kim sot cu trc lin kt chui (sao, lc, nhnh), thnh phn (khi, dc, xen k, thng k), v chc nng kt thc cho mt ln phm vi hon ton polymerizable monomers.17 ,2024 Trc n lc vi cht xc tc khng ng nht v khi khng hiu qu t successful.25 ATRP l trong cc lnh vc pht trin nhanh nht ha hc, vi s lng xut bn phm xp x tng gp i mi nm. Theo Khoa hc Finder Scholar, 7 giy t c cng b trn ATRP vo nm 1995, 47 vo nm 1996, 111 vo nm 1997, 150 vo nm 1998, 318 Nm 1999, v hn 300 vo nm 2000. Ngoi ra, nhiu giy t bng cch s dng khi nim ATRP nhng khng s dng Tn ATRP c xut bn (thay th danh mc bao gm kim loi chuyn tip qua trung gian sng cc oan trng hp, qu trnh chuyn i xc tc kim loi sng trng hp gc t do, nguyn t chuyn trng hp, vv). II. Ghi nh my mc ca Atom Chuyn Radical trng hp A. Cc thnh phn Nh mt h thng a thnh phn, ATRP bao gm monomer, mt khi vi mt chuyn nhng (Gi) halogen, v cht xc tc (bao gm mt loi kim loi chuyn tip vi bt k ligand thch hp). i khi mt ph gia c s dng. i vi mt thnh cng ATRP, cc yu t khc, chng hn nh dung mi v nhit , cng phi c xem xt. 1. Monome Mt lot cc monome c c thnh cng polyme ho bng cch s dng ATRP. Monome in hnh bao gm styrenes (meth) acrylates, (meth) acrylamides, v acrylonitrile, trong c cha nhm th, c th n nh radicals.22 tuyn truyn, 23 ring-m trng hp cng c successful.26, 27 Ngay c theo cc iu kin tng t bng cch s dng cng mt cht xc tc, monomer tng c chuyn giao nguyn t duy nht ca n hng s cn bng v hot ng ca n khng hot ng loi. Trong trng hp khng c bt k phn ng ph khc hn so vi chm dt trit bi khp ni hoc disproportionation, tm quan trng ca cc hng s cn bng (Keq) kact / kdeact) xc nh t l trng hp. ATRP s khng xy ra hoc xy ra rt chm nu hng s cn bng l qu nh. Ngc li, qu ln mt hng s cn bng s dn n mt lng ln s lng chm dt v mt gc t do cao tp trung. iu ny s c km theo mt lng ln s lng tt trng thi qu trnh oxy ha kim loi cao hn phc tp;3

s thay i trng thi cn bng i vi loi khng hot ng v c th kt qu ny c v chm hn polymerization.28 monomer Mi s hu gc t do ni ti ca tc lan truyn. Nh vy, cho mt monomer c th, tp trung tuyn truyn Cc gc t do v t l Chm dt hot trit cn phi c iu chnh duy tr kim sot trng hp. Tuy nhin, k t khi ATRP l mt qu trnh xc tc, v tr tng th ca s cn bng khng ch ph thuc n 2. Qu trnh chuyn i kim loi xc tc ATRP Atom Chuyn Radical trng hp ha hc Nhn xt, nm 2001, Vol. 101, s 9 nm 2923 Ti v ca Nguyn M vo ngy 30 thng 8 nm 2009 | http://pubs.acs.org Ngy xut bn (Web): Thng Chn 12, 2001 | doi: 10.1021/cr940534g cc gc t do (monomer) v cc loi khng hot ng, nhng cng c th c iu chnh bng s lng v phn ng ca cht xc tc kim loi chuyn tip (x. eq 2) 2. Khi Vai tr chnh ca ngi khi xng l xc nh s ang pht trin cc chui polymer. Nu bt u l nhanh chng v chuyn giao, chm dt khng ng k, th s cc dy chuyn ang pht trin l khng i v bng nng khi ban u. Cc l thuyt trng lng phn t hoc mc trng hp (DP) tng h tng vi nng ban u khi xng trong mt trng hp sng (eq 1). Hnh 1 minh ha mt s gia tng tuyn tnh phn t trng lng vi chuyn i. ng thi, polydispersities (Mw / Mn) gim vi chuyn i, ty thuc t l tng i Chm dt hot (x. eq 3). Trong ATRP, alkyl halogenua (RX) thng c s dng nh ngi khi xng v t l ca cc phn ng trng hp l ln u tin trt t i vi nng ca RX. c c cc polyme c xc nh vi thu hp phn t phn phi trng lng, nhm halogen, X, phi di chuyn nhanh chng v c chn lc gia ngy cng tng dy chuyn v phc tp qu trnh chuyn i kim loi. Nh vy n nay, khi X hoc l brom, clo, cc phn t kim sot cn nng l tt nht. Iodine hot ng tt cho acrylate polymerizations trung gian-ng ATRP29 v c tm thy dn n trng hp kim sot styrene ruthenium v rhenium-da trn ATRP.30, Flo 31 c khng c s dng bi v tri phiu CF l qu mnh tri qua s phn tch homolytic. Mt s pseudohalogens, c bit thioxyanat v thiocarbamates c s dng thnh cng trong trng hp ca acrylates v styrenes.29, 32,33 Bt u nn c nhanh chng v s lng vi mt tt khi xng. Ni chung, bt k alkyl halogenua vi Cc cht kch hot cc-bon-R, chng hn nh aryl, cacbonyl, hoc nhm allyl, c kh nng c th c s dng nh ATRP khi. Polyhalogenated hp cht (v d: CCl4 v CHCI3) v cc hp cht vi mt yu R-X tri phiu, chng hn nh N-X, S-X v O-X, cng c th c s dng ATRP khi. Khi phn na khi gn lin vi loi i phn t, macroinitiators c hnh thnh v c th c s dng tng hp khi / ghp copolymers.21 Tng t nh vy, hiu qu ca khi / ghp copolymerization c th thp nu t l r rng lin tc tuyn truyn nh hn so vi homopolymerization tip theo. Cn lu , tuy nhin, l tri phiu R-X c th c ct khng ch homolytically nhng cng heterolytically, ph thuc ch yu vo cu trc khi v s la chn ca cht xc tc kim loi chuyn tip. i vi V d, phn ng ph c quan st cho coppermediated ATRP ca p-methoxystyrene, c th do chia tch heterolytic ca CX tri phiu hoc qu trnh oxy ha ca cc gc t do tng ng carbocation.14, 34 3. Cht xc tc C l thnh phn quan trng nht ca ATRP l cht xc tc. N l cha kha ATRP k t khi n xc nh v tr ca cc nguyn t chuyn trng thi cn bng v s nng ng trao i gia cc loi khng hot ng v hot ng. C mt vi iu kin tin quyt cho mt cht xc tc kim loi chuyn tip c hiu qu. u tin, cc trung tm kim loi phi c t nht hai d dng trng thi xi ha c th truy cp c ngn cch bi mt in t. Th hai, cc trung tm kim loi cn phi c hp l mi quan h i vi halogen. Th ba, s phi hp phm vi xung quanh kim loi nn c m rng khi qu trnh oxy ha chn lc ph hp vi mt (gi) halogen. Th t, phi t nn phc tp kim loi tng i mnh m. Cui cng, v tr v ng lc ca s cn bng ATRP cn ph hp cho cc h thng c th. Mt lot cc -kim loi phc hp qu trnh chuyn i c nghin cu nh ATRP cht xc tc v s c tho lun chi tit hn sau ny trong bi vit ny. 4. Dung mi ATRP c th c thc hin vi s lng ln, trong gii php, hoc trong mt h thng khng ng nht (v d, nh tng, nh ch). Cc dung mi khc nhau, chng hn nh benzene, toluene, anisole, diphenyl ether, ethyl acetate, acetone, dimethyl formamide (DMF), ethylene cacbonat, ru, nc, carbon dioxide, v nhiu ngi khc, c c s dng cho cc monome khc nhau. Dung mi Mt i khi cn thit, c bit l khi cc polymer thu c l khng ha tan trong monomer ca n (v d, polyacrylonitrile). Mt s yu t nh hng n s la chn dung mi. Chui chuyn giao cho dung mi nn c ti thiu. Ngoi ra, tng tc gia dung mi v h thng cht xc tc c xem xt. Catalyst ng c. dung mi (v d nh carboxylic acid hoc phosphine trong copperbased ATRP) phn ng ph 35 v dung mi h tr,4

chng hn nh loi b HX t halogenua polystyryl, m l r rt hn trong mt dung mi cc, 36 nn c gim thiu. Kh nng rng cu trc ca cht xc tc c th thay i trong cc dung mi khc nhau cng cn c thc hin vo xem xt. V d, ATRP n-butyl acrylate vi CuBr (bpy) 3 (bpy) 2,2 bipyridine; v bn di cc k hiu phc tp ch phn nh stoichiometry ca thuc th thm vo v khng cu trc phc tp) nh cht xc tc thc hin ethylene cacbonat c tm thy tin hnh nhiu nhanh hn so vi bulk.37 thay i c cu t mt dimeric halogen-cu ni Cu (I) loi vi s lng ln h thng mt monomeric Cu (I) loi trong ethylene cacbonat c xut gii thch s chnh lch t gi. Nng cao t l tng t trong cc phng tin truyn thng cc quan st sau t khc nhau studies.38-40 phng tin truyn thng Polar cng c th gip ha tan cht xc tc. V d, ng nht ATRP s dng CuBr (bpy) 3 t c s dng 10% v / v DMF.41 Hnh 1. S i din ca s pht trin ca trng lng phn t v polydispersities vi chuyn i cho mt trng hp sng. DP) [M] 0 / [khi] 0 ? chuyn i (1) 2924 Ha cht, nm 2001, Vol. 101, s 9 Matyjaszewski v Xia Ti v ca Nguyn M vo ngy 30 thng 8 nm 2009 | http://pubs.acs.org Ngy xut bn (Web): Thng Chn 12, 2001 | doi: 10.1021/cr940534g 5. Nhit v thi gian phn ng T l ca phn ng trng hp trong ATRP tng theo nhit tng do s gia tng ca c hai cng tc tuyn truyn trit t l khng i v nguyn t chuyn giao hng s cn bng. Nh l mt kt qu ca kch hot nng lng cao hn cho cng tc tuyn truyn trit hn so vi vic chm dt trit , kp / kt t l cao hn v kim sot tt hn ("livingness") c th c quan st thy nhit cao hn. Tuy nhin, chui chuyn giao v phn ng pha bn kia tr nn r rt hn cao temperatures.36, 42 Nhn chung, ha tan tng cht xc tc nhit cao hn; Tuy nhin, cht xc tc phn hy cng c th xy ra vi nhit increase.43, 44 nhit ti u ph thuc ch yu vo cc monomer, cht xc tc, v trng lng phn t mc tiu. Ti chuyn i monomer cao, t l tuyn truyn chm li ng k, tuy nhin, t l bt k phn ng ph khng thay i ng k, nh hu ht trong s l monomer nng c lp. Thi gian phn ng ko di n gn monomer hon thnh chuyn i khng c th lm tng polydispersity ca polymer cui cng nhng s gy ra mt mt cui groups.45 V vy, c c polyme cao cui cng nhm chc nng hoc sau tng hp copolyme khi, chuyn i khng c vt qu 95% trnh mt mt nhm cui. 6. Ph gia Ph gia i khi rt cn thit cho mt thnh cng ATRP. V d, mt axit Lewis, chng hn nh nhm v alkoxides kim loi khc, l cn thit cho mi trng c iu chnh trng hp ca MMA xc tc bi RuCl2 (PPh3) 3 hoc systems.15, 46,47 trng hp Khng c hoc rt chm c quan st trong s vng mt ca Lewis axit kch hot. C l, hp cht nhm c th kch hot v n nh cht xc tc trong cao hn qu trnh oxy ha state.46 trng hp trong s hin din ca dung mi phn cc nh nc c th c tng tc. 39 S hin din ca nucleophiles mnh nh phosphines i khi c th chm dt qu trnh. 35 B. tiu biu Hin tng hc 1. S vn ng Cc ng lc hc ca ATRP c tho lun y bng cch s dng ng qua trung gian ATRP l mt v d. Thuc v c giI iu tra vo ATRP da trn kim loi khc h thng d kin s mang li kt qu tng t. Theo n 2 bng cch s dng gi nh rng ng gp ca chm dt tr nn khng ng k do cc gc t do lin tc effect7, 48 (PRE) (c bit l PRE49 chui di ph thuc) v s dng mt xp x trng thi cn bng nhanh chng, l cn thit cho cc polydispersities quan st thp, php lut t l (eq 2, cf. n 1 cho li gii thch ca tt c cc biu tng) cho mATRP c th c bt ngun nh sau. Hnh 2 cho thy mt s thay i in hnh tuyn tnh chuyn i mvi thi gian trong h ta semilogarithmic. Nh vy mt hnh vi ch ra rng c mt s tp trung lin tc mca cc loi ang hot ng trong cc phn ng trng hp v ng hc u tin theo n t hng lin quan n monomer. Tuy nhin, k t khi chm dt lin tc xy ra, nng ca cc tng cc loi Cu (II) v lch t tuyn tnh c th c quan st. i vi trng hp l tng vi chm dt chui di c lp, PRE ng hc ngha l m mu semilogarithmic monomer thi gian chuyn i vs s m 2 / 3 nn c linear.7 Tuy nhin, mt semilogarithmic tuyn tnh ct truyn thng c quan st thy. iu ny c th l do s vt qu ca loi Cu (II) trnh by ban u, mt chainlength t l chm dt ph thuc vo h s, v khng ng nht ca h thng phn ng do b hn ch ha tan ca cc phc ng. N cng c th mm bt u t lin tc c th sn xut cc gc v bi thng cho termination.50, 51 Tng t nh vy, bn5

ngoi mn t hng cho ngi khi v Cu (I) mloi cng c th b nh hng bi cc PRE.52 mKt qu t cc nghin cu ng hc ca ATRP styrene, 35 mmethyl acrylate (MA), 53 v methyl methacrylate m(MMA) 54,55 di iu kin ng nht cho thy rng tc ca phn ng trng hp l ln u tin t hng vi mlin quan n monomer, khi u, v Cu (l) phc tp nng . Nhng quan st ny l tt c ph hp ca php lut v t l ngun gc (eq 2). Cc kinetically t l ti u ca phi t ng trong trng hp ca c hai styrene v MA c xc nh l 2:1. Di y t l ny t l trng hp thng chm hn, v cao hn t l ny trng hp t l vn khng i. Cn lu rng t l ti u c th khc nhau i vi nhng thay i trong monomer, counterion, phi t, nhit , v khc factors.43, 54,56 Chnh xc ng hc php lut v deactivator (X-CuII) phc tp hn do cc th h t pht Cu (II) thng qua cc gc t do lin tc effect.7, 35,52 Trong nguyn t chuyn bc, mt phn ng hu c gc t do l mc to ra cng vi mt n nh Cu (II) loi c th c coi nh l mt metalloradical lin tc. Nu mban u tp trung deactivator Cu (II) trong trng hp l khng ln m bo mt nhanh t l Chm dt hot (kdeact [Cu (II)]), sau khp ni cc gc hu c s xy ra, dn n mt tng nng Cu (II). Qu trnh ny c c quan st thc nghim bng cch s dng IH NMR, UVvis, EPR, v GC-MS techniques.35, 57 Vi mi trit chm dt s kin, 2 equiv ca Cu (II) s hnh thnh khng th phc hi. Trit chm dt nhanh chng xy ra cho n khi mt s lng y ca deactivator Cu (II) c hnh thnh v nng gc t do tr nn thp. Trong iu kin nh vy, tc m cc gckt hp (kt [RL] 2) s tr nn chm hn so vi Rp) kp [M] [P *]) kpKeq [M] [I] 0 ? [Cui] / [X - CuII] (2) Hnh 2. S i din ca s ph thuc ca vic chuyn i thi gian tuyn tnh v semilogarithmic ta . Atom Chuyn Radical trng hp ha hc Nhn xt, nm 2001, Vol. 101, s 9 nm 2925 Ti v ca Nguyn M vo ngy 30 thng 8 nm 2009 | http://pubs.acs.org Ngy xut bn (Web): Thng Chn 12, 2001 | doi: 10.1021/cr940534g tc m cc gc t do phn ng vi ng (ll) phc tp (kdeact [RL] [Cu (II)]) trong mt qu trnh v hiu ha v / kim sot trng hp "sng" s tin hnh. mThng thng, mt phn nh (5%) ca tng s pht trin cc chui polymer s c chm dt trong thi gian u giai on ca s trng hp, nhng a s cc dy chuyn (90%) s tip tc pht trin thnh cng. Nu mt s lng nh ca deactivator (10 mol%) thm vo ban u trng hp, sau t l cc chui kt thc c th c gim ng k. 20,57 Hiu qu ca Cu (II) trn trng hp c th thm phc tp bi tnh ha tan ngho ca n, gim chm bng phn ng vi monome 1,2dihaloadducts, hoc t c lp ban u h thng nh styrene v cc monomers.51, 58 2. Trng lng phn t Tng t nh mt trng hp sinh hot tiu biu, trng lng phn t trung bnh ca polymer c thc hin bi mt ATRP c kim sot tt c th c xc nh trc. t l ca monomer tiu th v khi (DPN) [M] / [I] o. DP) mc trng hp), trong khi, duy tr mt trng lng phn t tng i hp phn phi (1.0 100 C) c a thch cho styrene ATRP. Phn ng ny c th c thc hin trong s lng ln hoc s dng mt dung mi, nhng s n nh ca nhm cui halogen hin th mt dung mi pht m ph thuc nh chng minh bi cc nghin cu m hnh s dng 1-phenylethyl bromide. Kt qu l, cc dung mi khng cc c khuyn ngh cho styrene ATRP.36 Polystyrenes vi trng lng phn t (Mn) khc nhau, t 1000 100 000 vi polydispersities thp c chun b. Kim sot trng lng phn t tt hn l thu c nhit thp hn, c l do mt ng gp thp hn nhit t initiation.42, 58 Ngoi ra, mt lot cc dn xut styren Cc cht khc nhau vo vng thm c polyme trong mt fashion.34 c kim sot tt c xc nh p acetoxystyrene c chun b, v tip theo thy phn dnh tan trong nc nhiu (vinylphenol). 102 Ni chung, styrenes vi electron-rt Cc cht polymerize nhanh hn. Cc Hammett tng quan cho ATRP ca styrene cung cp F) 1.5 so F) 0.5 cho cc hng s tuyn truyn cc oan. iu ny cho thy rng, cn bng chuyn giao nguyn t thay i theo hng pha loi hot ng cho styrenic monome mang electron-rt nhm. Hnh vi ny c gii thch bi ATRP cao hn phn ng ca cc halogenua th benzylic vi electronwithdrawing groups.103 n 4 cho thy mt s styrene cc cht dn xut thnh cng polyme ATRP. 2. Acrylates ATRP kim sot acrylates c bo co cho ng, 16,18,53 ruthenium, 104 v h thng da trn st. 105 ng xut hin c cp trn khc kim loi chuyn tip trong sn xut c xc nh polyacrylates9

vi polydispersities mt tng i thp thi gian ngn. iu ny mt phn l do Chm dt hot nhanh cc gc acrylic tng cc cupric halogenua. Thng thng polymerizations c tin hnh s lng ln vi mt khi bromopropionate 2-alkyl. Welldefined polyacrylates vi Mn ln n 100 000 Mw / Mn 100 C. Ngoi ra trng hp gii php, gip gi cho nng ca pht trin thp gc t do. Trong iu kin so snh, ng ATRP qua trung gian ca MMA hin th mt cch ng k hng s cn bng cao hn khi so snh vi styrene v MA. Kt qu l, pha long cao hn v mt thp hn nng cht xc tc nn c s dng cho cc MMA trng hp. Bt u ng mt vai tr quan trng trong ATRP ca MMA. Khi kin tt nht bao gm sulfonyl chlorides111 v 2-halopropionitrile98 bi v nhng khi c hng s tc ln r rng ca bt u (cao nguyn t chuyn trng thi cn bng hng s). Xc nh PMMA c th c chun b trong vng trng lng phn t khong t 1000 180 000. Mt lot khi, bao gm c chloromethanes, R-chloroesters, R-chloroketones, v R-bromoesters, nghin cu ATRP ruthenium qua trung gian ca MMA.120 CCl3COCH3, CHCl2COPh, v dimethyl 2-bromo- 2,4,4-trimethylglutarates nm trong s nhng ngi khi xng tt nht, nng sut PMMA vi kim sot phn t trng lng v polydispersities thp (Mw / Mn) 1,1-1,2). Cc nghin cu tng t cng c thc hin cho cc h thng da trn Cu. 121.122 Cn lu rng mt s trong nhng khi qu tch cc cho cc h thng da trn ng v dn n vic chm dt qu mc hoc pha bn kia reactions.123 Este methacrylic cng c c thnh cng polyme. Chng bao gm n-Butyl methacrylate, 55,77,88,124 2 - (dimethylamino) ethyl methacrylate (DMAEMA), 125 2-hydroxyethyl methacrylate (Hema) 104.126 v silyl bo v Hema, 127 methacrylic axit trong bo v alkyl form128 hoc nh natri ca n mui, 129 methacrylates vi mt (ethylene oxide) oligo substituent, 39 v este methacrylic flo. 82.110.130 n 6 minh ha cc v d ca methacrylates polyme ho bng ATRP. 4. Acrylonitrile Kim loi trung gian kim sot trng hp cc oan acrylonitrile c cho n nay ch c bo co cho ng qua trung gian ATRP.66, 131.132 l cn thit s dng mt dung mi v polyacrylonitrile khng ha tan trong monomer ca n. DMF l mt dung mi tt cho polyacrylonitrile; Tuy nhin, n cng c th phc tp vi ng v tt cc cht xc tc. Thnh cng polymerizations c thc hin trong cacbonat ethylene trong s hin din ca phc tp CuBr 2 (bpy) bng cch s dng R-bromopropionitrile l ngi khi xng nhit t 44-64 C. Cc CuBr (bpy) 2 cht xc tc c ha tan trong mi trng trng hp cc mnh, v h thng ng nht. Cc nh ngha polyacrylonitrile vi Mw / Mn 10 000. S la chn ca pH v khi l rt quan trng. pH ti u nm gia 8 v 9, dng nh l mt s cn bng gia cng tc tuyn truyn gim tc pH cao v proton cnh tranh ca phi t pH thp. Ngoi ra chuyn i thp, v khi to hiu qu thu c khi natri 2 bromoisobutyrate c s dng nh khi. Khc c tnh axit monome nh vinylbenzoate natri cng c thnh cng polyme trong dung dch nc phng tin truyn thng s dng mt tng t methodology.143 Ngoi ra, poly (meth) axit acrylic c th c chun b bng cch trng hp monome c bo v nh vy nh trimethylsilyl methacrylate, tert-butyl methacrylate, tetrahydropyranyl methacrylate, v benzyl methacrylate.144 7. Linh tinh monome Pyridin c cha polyme hu ch cho khc nhau cc ng dng nh polyme tan trong nc v phi hp thuc th cho11

cc kim loi chuyn tip. C hai 4-vinylpyridine (4VP) v poly (4-vinylpyridine) (P4VP) c th hot ng nh phi t phi hp cho cc kim loi chuyn tip v cnh tranh cho cc rng buc ca cc cht xc tc kim loi ATRP. Bng cch s dng mt mnh m phi hp phi t nh Me6TREN, xc nh P4VP thu c 40 C bng cch s dng mt cht xc tc da trn ng system.145 Xen k copolyme ca isobutene vi MA, BA, v AN c chun b bng cch s dng CuBr (bpy) 3 cht xc tc v bromide 1 phenylethyl nh khi 50 C.146 khi lng phn t th nghim gn vi cc gi tr l thuyt, t 4000 n 50 000. Polydispersities c tng i cao (Mw / Mn? 1.50). Bng chng v trnh t lun phin v cc tacticity ca isobutene vi MA c cung cp bi phn tch 1H NMR. Chun b xen k copolymer vi MA l mt cht n hi vi mt syndiotactic cu trc vt tri v thy tinh thp qu trnh chuyn i nhit (Tg -30 C). Xen k copolymerizations maleimides styrene22 ,146-149 v MMA150 c thc hin bng cch s dng da trn ng ATRP. S gia tng tuyn tnh ca Mn vi s chuyn i c quan st ln n Mn? 13 000, Mw / Mn khong 1,16-1,36. N-(2-acetoxyethyl) - maleimide c tm thy copolymerize nhanh hn N-phenylmaleimide.147 Trng hp ca clorua vinylidene v isoprene 17 do ng qua trung gian ATRP cng c thc ra ngoi. Kim sot trng hp vinyl acetate (VOAc) bi ATRP vn cn y thch thc, phn ln l do nh nguyn t chuyn trng thi cn bng constant.151 Tuy nhin, copolymerization thnh cng ca VOAc MA c reported.99 Ngoi ra, VOAc c thnh cng khi copolymerized bng cch kt hp ATRP vi cc phn ng trng hp processes.151, 152 ATRP ca alkene halogen ha cha c bo co chi tit. Trng hp m vng c c thnh cng monome nhiu, c bit l i vi nhng ngi Cc cht c gc t do n nh. Tim nng copolymerization ca cc monome ny s dn n polyme vinyl vi mt lin kt hydrolyzable trong chnh chain.26, 153 Mt s v d v cc monome khc (ng) polyme bng cc monome ATRP c th hin trong n 7. Tm li, mt lot cc monome c c thnh cng polyme di iu kin ATRP sn lng polyme c xc nh r. i vi mt monomer phi tri qua ATRP, iu quan trng l phi n nh nhm (v d, phenyl hoc cacbonyl) tip gip vi cc gc carbon sn xut mt nguyn t ln chuyn hng s cn bng nhng khng nh hng vi cc gc t do pht trin v h thng xc tc. Ngoi ra, n l cn thit iu chnh cc phn ng iu kin (nng , nhit , cht xc tc) c c mt nng thch hp cn bn cho mt c th monomer. 8. Tm tt v Outlook ATRP thnh cng trong kim sot trng hp styrenes, acrylates, v methacrylates v mt s tng i phn ng monome chng hn nh acrylamides, vinylpyridine, v acrylonitrile. Atom Chuyn Radical trng hp ha hc Nhn xt, nm 2001, Vol. 101, s 9 nm 2931 Ti v ca Nguyn M vo ngy 30 thng 8 nm 2009 | http://pubs.acs.org Ngy xut bn (Web): Thng Chn 12, 2001 | doi: 10.1021/cr940534g Tuy nhin, c hai loi chnh cc monome khng c thnh cng polyme bng ATRP. Monome c tnh axit khng v chng c th protonat phi t v hnh thnh cc mui tng ng carboxylate.Hin c tin b trong lnh vc ny, v methacrylic axit trong cc hnh thc trung lp ca mui natri c polyme. Mt cch tip cn tng t c bo co monome khc c tnh axit. V nguyn tc, s dng t hn phi t c bn (oxy v lu hunh), m s cng phc tp mnh m, c th ngn nga mt cc phi t. Ngoi ra, cc axit c th c s dng nh cc phi t bn thn: succinates st hoc halogenua c bo co l ATRP cht xc tc. Dn xut halogen ha alkene, alkyl-thay th olefin, v este vinyl l hin nay kh nng chng trng hp bi ATRP. H thuc v mt lp cc monome ni ti rt thp phn ng trng hp cc oan v phn ng b sung trit v c th c rt thp ATRP hng s cn bng. polymerize, n s l cn thit s dng cc cht xc tc rt cao phn ng v ni chung l gim tiu cc tim nng, nhng iu ny c th c i km vi gim cc gc t do carbanions v hnh thnh c kim loi. Loi ny c th phn ng bng mt phi hp ng hn l thng qua cc gc t do trung gian. Nhng loi cng c th c hydrolytically v cht xc tc km n nh hn c th rt nhy cm vi oxy. Phm vi ca cc monome polymerizable bi ATRP ln hn so vi truy cp bng nitroxide qua trung gian trng hp, v n bao gm ton b gia nh methacrylates. Tuy nhin, qu trnh chuyn giao thoi ha, vi phng php b l hin nay hu ht thng c s dng, cho php trng hp ca monome hn hn ATRP. C l ATRP cht xc tc mi c th lm gim bt vn ny. Tuy nhin, n phi c nhn mnh mi nhm monome c th l tt nht ph hp vi mt c ch c th. V d, isobutene v ete vinyl tt nht ph hp vi trng hp cation, R-olefin v c th phi hp dienes, v / hoc anion trng hp, trong khi cc monome cc nh vy (meth) - acrylates dng nh ph hp vi c ch gc t do tt nht. D. ATRP khi Nh tho lun trc y, s lng khi trong ATRP xc nh trng lng phn t cui cng polymer ti monomer chuyn i y . a chc nng khi xng c th cung cp s pht trin ca chui trong hng dn mt s (x. phn III.C). Nhanh chng bt u quan trng l c c cng c xc nh polyme thp12

polydispersities. Mt lot cc khi xng, thng alkyl halogenua, c s dng thnh cng trong ATRP. Nhiu cc loi khc nhau ca halogen ha cc hp cht c tim nng khi xng v c tho lun di y da trn ca h cu trc. 1. Dn xut halogen ha alkan Alkan Dn xut halogen ha, chng hn nh CHCl3 hoc CCl4, thng c s dng trong chuyn Ngoi ra nguyn t gc t do v l nhng ngi u tin nghin cu nh initiators.15 ATRP, 16 Trong ATRP ruthenium xc tc ca MMA, phn t trng lng ca polyme tng tuyn tnh vi vic chuyn i, tuy nhin, chuyn i monomer cao, trng lng phn t lch t l thuyt values.124 Cc polyme thu c monomodal polydispersities thp (khong 1,3). Ngc li, di-hoc monochloromethanes khng th polymerize MMA di conditions.120 tng t CCl4 cng c s dng trong cc h thng xc tc, bao gm one.18 Cu-Khi CuCl (bpy) 3 c s dng nh cc cht xc tc cho cc ATRP styrene 130 C, CCl4 c tm thy hot ng nh mt bifunctional initiator.121 Mt ln na, lch ca trng lng phn t t gi tr l thuyt c quan st thy, v iu ny c d kin gii thch bi cc chui b sung to ra kt qu t s kch hot ca cc trung tm dichloromethylated phn na m tri qua -scission.121 Kim sot trng lng phn t l c th s dng CHCl3 cho h thng CuCl 3 (bpy), trong khi di v monochloromethanes dn polymerizations khng kim sot c. 18 Trong cc h thng ng nht, CCl4 l i khi km hiu qu do ngoi cng lnh vc tim nng in t-chuyn giao (OSET) phn ng v gim ca cc gc t do anion (x. phn II.I). Chm b sung cc cht xc tc h thng khi dng nh ci thin bt u efficiency.42 CCl4 v Ni {o, o - (CH2NMe2) 2C6H3} Br lm cht xc tc, th nghim trng lng phn t ca PMMA tng monomer chuyn i, nhng cho thy lch chuyn i cao, 113 tng t nh hp ruthenium system.15 lch ca trng lng phn t cng c quan st cho FeCl2 (PPh3) 2 xc tc system.116 CCl3Br thnh cng trong vic khi xng trng hp kim sot MMA xc tc RuCl2 (PPh3) 3,83 NiBr2 (PPh3) 2,44 NiBr2 (PnBu3) 2114 hoc Ni (PPh3) 4,154 Tuy nhin, vi h thng 2 Ni (II) / (PPh3), kt hp khc ca ngi khi xng v cht xc tc, chng hn nh CCl3Br/NiCl2- (PPh3) 2, CCl4/NiBr2 (PPh3) 2, hoc CCl4/NiCl2 (PPh3) 2, kt qu trong bn phn phi trng lng phn t hai nh ti High MMA conversions.44 2. Benzylic Halogenua Benzyl-thay th halogenua khi hu ch cho trng hp styrene v cc dn xut ca n do ging cu trc ca chng. Tuy nhin, h khng n 7. Linh tinh monome (co) polyme bng ATRP 2932 Ha cht, nm 2001, Vol. 101, s 9 Matyjaszewski v Xia Ti v ca Nguyn M vo ngy 30 thng 8 nm 2009 http://pubs.acs.org Ngy xut bn (Web): Thng Chn 12, 2001 | doi: 10.1021/cr940534g trng hp ca monome phn ng ATRP chng hn nh MMA. V d, s dng CuCl (DNbpy) 2 l cht xc tc, khi u khng hiu qu quan st thy khi clorua 1phenylethyl lm vic l ngi khi xng cho s trng hp ca MMA.123 PMMA vi khi lng phn t cao hn nhiu so vi gi tr l thuyt v polydispersities cao (Mw / Mn) 1,5-1,8) thu c. Ngc li, mt kim sot tt trng hp c thc hin vi clorua benzhydryl (Ph2CHCl) l ngi khi xng iu kin tng t. Trong thc t, th h cp tin qu nhanh lm chm Ngoi ra clorua benzhydryl l cn thit trnh mt ng gp quan trng ca biradical khng th o ngc chm dt sm ci thin polymerization.123 hiu qu bt u cho ATRP ca MMA s dng tiu hc v trung hc halogenua benzylic c th bng cch s dng vic trao i halogen concept.155 Polyhalogenated halogenua benzylic c s dng cho ATRP ca MMA xc tc bi RuCl2 (PPh3) 3/Al- (OiPr) 3,120 PMMA vi polydispersities rt thp thu c khi Ph2CCl2 c s dng nh khi. Trong Ngc li, PhCCl3 dn n trng lng phn t hai mt phn phi bao gm hai phn b hp phn s, cao hn gp i so vi phn t trng lng ca PhCHCl2 other.120 cng c c s dng trong CuATRP styrene v MMA, r rng cung cp hai hng pht trin ca cc cao phn t chains.156 n 8 minh ha mt s v d ca cc dn xut halogen alkan v halogenua benzylic s dng thnh cng trong ATRP. 3. R-Haloesters R-haloesters khc nhau c s dng thnh cng bt u kim sot tt ATRP. Ni chung, R-haloisobutyrates sn xut gc t do bt u nhanh hn hn tng ng vi R-halopropionates do n nh tt hn ca cc gc t do c to ra sau khi bc tru tng halogen. Nh vy, bt u chm thng xy ra nu R-halopropionates c s dng bt u trng hp ca methacrylates. Ngc li, R bromopropionates khi tt choATRP ca acrylates do ging cu trc ca h. Trong tm kim ca h khi kin tt hn trong rutheniummediated ATRP, Sawamoto et al. kim tra ba R-bromoesters cu trc khc nhau ( n 9) 0,120 Malonate vi hai este geminal to ra nhanh hn bromoisobutyrate-2 gc t do v dn n thp hn polydispersities. M hnh dimeric ca kt thc chui khng hot ng (dimethyl 2-bromo-2 ,4,4-trimethylglutarate) khi to mt trng hp nhanh hn v cung cp cho PMMA vi13

polydispersities thp hn R-bromoisobutyrate, c th do s cng thng tr li c hiu lc; 54.157.158 pht hnh ca dng steric ca loi khng hot ng trong rehybridization t cc sp3 cu hnh sp2 dn n mt trng thi cn bng cao hn khng i. M hnh dimeric cng c s dng trong ATRP ca MMA xc tc NiBr2 (PPh3) 2115 clorua tng t ca cc hp cht m hnh dimeri dn n trng hp kim sot ca MMA styrene qua trung gian ca mt ruthenium na metallocene loi complexes.159 Cc dn xut malonate km hiu qu hn trong Cu- ATRP, c l do cp trc OSET qu trnh. Chm b sung cc cht xc tc khi xng gii php trong monomer ci thin kim sot rt nhiu. 42 R-Haloesters vi cc nhm khc nhau chc nng km theo c th d dng c chun b thng qua mt n gin phn ng este ha ca axit thch hp halogenua. K t khi ATRP c th chu ng chc nng khc nhau nhm, cui cng cng c xc nh chc nng polyme c c chun b thun tin m khng cn phn ng bo v thm. Mt lot cc chc nng, chng hn nh hydroxy, epoxy, allyl, vinyl, -lacton, v axit cacboxylic c gii thiu vo R-end ca polymer bng cch s dng ca mt khi chc nng v s c tho lun trong phn sau ( n 10) .99,128,160 Polyhalogenated R-haloesters (v d:, CCl3CO2CH3 v CHCl2CO2CH3) cng c p dng thnh cng l ngi khi xng cho ATRP ca MMA xc tc RuCl2 (PPh3) 3/Al (OiPr) 3,120 Multiarm ngi sao ca PMMA c sn xut khi dichloroacetates a chc nng c s dng trong xc tc ruthenium-ATRP.161, 162 Benzyl hn hp v cc dn xut ester nh methyl Bromophenylacetate-R c s dng thnh cng trong trng hp dung dch nc ca 2 - (dimethylamino) ethyl methacrylate.163 4. R-Haloketones Mt R-bromoketone c s dng bt u kim sot trng hp MMA xc tc Ni {o, o - (CH2NMe2) 2C6H3} Br113 v Ni (PPh3) 4,154 Polyhalogenated R-haloketones (v d:, CCl3COCH3 v CHCl2COPh) l mt trong nhng ngi khi xng tt nht n 8. Mt s halogen ha alkan v Halogenua Benzylic s dng nh khi ATRP n 9. R-Bromoesters khc nhau s dng trong Ruthenium trung gian ATRP ca MMA n 10. i din chc nng khi C ngun gc t r-Haloesters Atom Chuyn Radical trng hp ha hc Nhn xt, nm 2001, Vol. 101, s 9 nm 2933 Ti v ca Nguyn M vo ngy 30 thng 8 nm 2009 | http://pubs.acs.org Ngy xut bn (Web): Thng Chn 12, 2001 | doi: 10.1021/cr940534g ATRP ca MMA xc tc ruthenium complexes.83, 120.159.164.165 polyme vi kim sot tt polydispersities thp (Mw / Mn C (O) R> C (O) hoc Ph>> Cl> Me. Nhiu nhm chc nng c th lm tnghot ng ca alkyl halogenua tetrachloride v d nh carbon,, benzhydryl dn xut, v malonates. i hc alkyl halogenua khi tt hn so vi trung nhng ngi thn, tt hn so vi cc halogenua chnh alkyl. Nhng c mt phn xc nhn bi cc php o gn y kch hot tc constants.171-173 Sulfonyl clorua cng cung cp bt u nhanh hn so vi tuyn truyn. (2) Th t chung ca sc mnh tri phiu trong alkyl halogenua R-Cl> R-Br> R-I. V vy, alkyl clorua nn c khi hiu qu nht valkyl iodides hiu qu nht. Tuy nhin, vic s dng alkyl iodides i hi phi c bin php phng nga c bit. H l nh sng nhy cm, c th hnh thnh cc khu phc hp iodide kim loi vi mt phn ng bt thng (v d, CuI2 l nhit ng khng n nh v khng th c c lp), tri phiu R-I c th c th c ct heterolytically, v c bin chng tim n ca qu trnh ATRP thoi ha transfer.174, 175 xa, v brm clo l halogen c s dng thng xuyn nht. Trong Nhn chung, cc halogen c s dng trong khi v Tuy nhin, cc halogen mui kim loi (v d, RBr / CuBr); n 11. V d Clorua Sulfonyl s dng nh khi ATRP 2934 Ha cht, nm 2001, Vol. 101, s 9 Matyjaszewski v Xia Ti v ca Nguyn M vo ngy 30 thng 8 nm 2009 | http://pubs.acs.org Ngy xut bn (Web): Thng Chn 12, 2001 | doi: 10.1021/cr940534g trao i i khi c th c s dng c c tt hn trng hp control.155 Trong mt hn hp nh tng bt u h thng, RX / Mt-Y (X, Y) Br hoc Cl), phn ln cc cc chui polymer c chm dt bi clo do mnh m hn alkyl clorua tri phiu. Nh vy, t l bt u c tng ln tng i so vi tuyn truyn v ethyl 2-bromoisobutyrate/CuCl dn n mt bettercontrolled trng hp ca MMA so vi s dng ethyl 2-bromoisobutyrate/CuBr.155 tng t Kt qu cng c quan st thy Ru-da ATRP.176 Phng php trao i halogen cng cho php vic s dng alkyl halogenua ca reactivities r rng l thp hn trong trng hp ca monome dng nh cao hn trng thi cn bng hng s. iu ny c bit quan trng cho s hnh thnh ca khi copolymers.177-180 Pseudohalogens (V d, SCN) cng c s dng trong ATRP.29, 33 Bt u s dng thiocyanate benzyl chm cho c hai styrene v MA, v Mn cao hn so vi l thuyt gi tr thu c. Thu c kt qu tt hn khi alkyl halogenua c s dng nh l nhng ngi khi xng v CuSCN l cht xc tc. Tng t, kim loi chuyn tip dithiocarbamates c s dng trong s hin din ca AIBN to ra iu khin o ngc ATRP ca styrene 120 C. Tha thun gia l thuyt v th nghim gi tr Mn thu c vi Mw / Mn ) 1.15-1.30.32 (3) bt u thnh cng trong ATRP c th ph thuc mnh m vo s la chn ca cht xc tc. V d, 2-bromoisobutyrophenone khi to cc iu khin trng hp ca MMA xc tc bi ruthenium hoc phc niken nhng khng c thnh cng c s dng trong ATRP ng qua trung gian. iu ny l gn gim kt qu electrophilic trit ng (I) loi nh l cht xc tc ng gim tim nng oxi ha kh. (4) Cc phng php, trt t Ngoi ra thuc th c th l rt quan trng. V d, chm b sung ca ngi khi clorua benzhydryl CuCl (dNbpy) 2-xc tc ATRP ca MMA to ra mt thp hn nng cc gc t do benzhydryl v do lm gim t l chm dt gia cc gc. 2-bromomalonate/CuBr diethyl h thng khi ATRP ca styrene, v trng hp c kim sot khi cht xc tc c b sung t t. khi / monomer gii php. iu ny trnh c kh nng gim malonyl trit bng ng (I) loi. N cng c th ng ngc nhin, nhng khng ng nht h thng xc tc c th cung cp hiu qu hn bt u hn so vi nhng ngi ng nht khi rt phn ng khi alkyl halogen c s dng, nhiu kh nng do chm gii th cc cht xc tc v do thp hn ca n tc thi tp trung. V d, CCl4 l mt khi styrene v MMA vi CuBr (bpy) 3 nh cht xc tc, 18 nhng ging nhau l khng ng s tht bng cch s dng CuBr (dNbpy) 2 xc tc h thng. Hiu qu bt u tng ln khi cc gii php cht xc tc l thm vo t t khi solution.428. Tm tt v Outlook Phm vi ca ngi khi cho ATRP l nhiu ln hn so vi cc phng php CRP khc. Trong thc t, nhiu ngi NMP v b thuc th c chun b t ATRP khi, tc l, kch hot halogenua alkyl hoc nucleophin chuyn (b) hoc by gc t do trong s hin din ca Cu (0) (NMP). Yu cu c bn cho mt khi ATRP tt l n cn phi c phn ng t nht l so snh vi cc sau hnh thnh chui pht trin. iu ny cng cho thy rng khng phi tt c ngi khi xng l tt cho tt c cc monome. iu ny l mt tiu ch v cng quan trng cho vic chun b copolyme khi. Khi d phn ng c th,sn xut cc gc qu nhiu, s chm dt ti giai on u. iu ny s lm gim hiu qu ca bt u, sn xut ra qu nhiu ca deactivator, v lm chm li qu trnh. C l mt trong s t cc trng hp ngoi l l mt lp halogenua sulfonyl chm dt tng i chm chm dt trit khng th o ngc. N l cn thit tng quan cu trc ca cc alkyl halogenua vi reactivities ATRP ca h. iu ny bao gm c phn alkyl (in t v steric hiu ng) v (gi) halogen. Phn ng ATRP bao gm khng ch cc BDE ca cc tri phiu CX, m cn halogenophilicity ca kim loi chuyn tip. Nh vy, phn ng tng quan cu trc nn bao gm c thnh phn cng nh nh hng ca dung mi v nhit . So snh cc m hnh v phn t cc hp cht cng l quan trng cng nh m rng h thng dy c so snh trong ni b v gia cc phn t tc dng. iu ny s c15

c bit quan trng cc k thut phn t phc tp cao phn t cu trc. Halogen nhm cui cng l mt phn c hu ca ATRP h thng. Chng c th c thay th bng nhiu phng php tng hp cung cp cc chc nng hu ch hn v cung cp halogen-min ph sn phm. Pseudohalogens chng hn nh (iso) thiocyanate v nhm azide c cng c s dng nh cc nhm cui cng trao i trong ATRP v kh hp dn, v chng c th c hydrolytically n nh hn v c th cung cp cc con ng trc tip polyme cui chc nng. C nhiu a chc nng kch hot halogenua cho php ng thi tng trng ca chui trong mt s hng dn , chi ngi sao, v cc i phn t bn chi. Phc kim loi chuyn tip E. Mt s khu phc hp kim loi chuyn tip c c p dng trong ATRP. Nh cp trc y, to ra ngy cng tng cc gc t, cc trung tm kim loi phi tri qua mt phn ng truyn in t vi cc tru tng ca halogen (gi) v m rng s phi hp hnh cu. Ngoi ra, phn bit ATRP t thng thng oxi ha kh trng hp khi xng v to ra mt qu trnh c iu chnh, qu trnh chuyn i oxy ha kim loi nn nhanh chng tt tuyn truyn chui polymer to thnh loi khng hot ng. Cc ng dng v phm vi ca transitionmetal khc nhau khu phc hp c tho lun theo nh k ca h nhm. 1. Nhm 6: Molypden v Chromium Mt lot cc khu phc hp lithium molybdat (V) [LiMo- (NAR) 2 (C-N) R] (C-N) C6H4 (CH2NMe2) -2; R) (CN), Me, CH2SiMe3, hoc p-tolyl), c s dng trong ATRP ca styrene s dng benzyl clorua nh khi ( n 12) 0,181 molybdat (V) phc hp to ti ch t phn ng tng ng molybdenum (VI) phc hp [Mo (NAR) 2 (C-N) R]. Polydispersities tng i cao (Mw / Mn 1,5?) thu c, v hiu qu ca clorua benzyl khi thay v ngi ngho (6-18%), c gn nhy khng kh cc lithium Atom Chuyn Radical trng hp ha hc Nhn xt, nm 2001, Vol. 101, s 9 nm 2935 Ti v ca Nguyn M vo ngy 30 thng 8 nm 2009 | http://pubs.acs.org Ngy xut bn (Web): Thng Chn 12, 2001 | doi: 10.1021/cr940534g molybdat (V), cc hp cht. Ngoi ra, mt phn ng ph xy ra trong ATRP; molybdat lithium (V) phn ng (R-chloroethyl) benzen v (R-bromoethyl) benzen v kt qu l s hnh thnh ca LiCl LiBr, tng ng. Cng c c mt bo co cho thy rng crom dn xut c th hot ng nh cht xc tc ATRP, nhng khng c bng chng h tr mt qu trnh cc oan, m cng c th xy ra thng qua mt anion / phi hp pathway.182 2. Nhm 7: Rhenium Rhenium thuc nhm 7 v cho thy cc c im ca qu trnh chuyn i sm v mun kim loi. Gn y, rhenium (V) iododioxobis (triphenylphosphine) (ReO2I (PPh3) 2) trong s hin din ca Al- (OiPr) 3 c bo co l mt cht xc tc hiu qu trng hp kim sot ca styrene s dng mt alkyl ioua nh initiator.30 Polymerizations thc hin nhit gia 30 v 100 C, vi phn ng nhanh hn nhit cao hn. Polydispersities thp hn nhit gim (Mw / Mn 1,50 100 C v 1,26 30 C). Welldefined polystyrenes vi Mn ln n 40 000 Mw / Mn? 1,1-1,2 c chun b vi s lng ln mc 80 C. Trong s iodide khi xng nghin cu, (CH3) 2C (CO2Et) I v CH3-CH (Ph), kt qu thp hn polydispersities hn CH3- CH (CO2Et) I. Ngoi ra, CH3CH (CO2Et) Ti l khi dn Mn hi cao hn so vi tnh ton gi tr trong giai on u ca s trng hp, cho thy bt u chm li t cc loi acrylate khi xng. 1H NMR cui cng nhm phn tch cho thy s hin din ca mt phn na khi (R) vo cui-R v mt i-t nguyn t vo cui-, c hai bt ngun t khi R-I. Th nghim dp tt cho thy thm methanol hoc nc khng c ch s trng hp, trong khi 2,2,6,6 tetramethylpiperidine-N-oxyl (TEMPO) ngay lp tc v hon ton ng ca phn ng. Tht th v, polystyrene dp tt vi TEMPO khng cho thy bt k TEMPO lin quan n nh trong NMR 1H. 1H NMR 13C v phn tch ca mt hn hp ca ReO2I (PPh3) 2 v TEMPO ch ra mt c th tng tc gia hai hp cht ny. l kt lun rng s trng hp khng tin hnh thng qua mt c ch ion, v mt gc con ng c xut. Tuy nhin, c th l cc phc rhenium t t to ra cc khi xng cc gc t do nhng kim sot ca cc kt qu trng hp t chuyn nhng thoi ha vi iodides alkyl. 175 s l hu ch phn tch cc Chm dt hot t l (VI) cc loi Re. 3. Nhm 8: ruthenium v st Ruthenium v st thuc v qu trnh chuyn i 8 nhm kim loi v c nghin cu trong nguyn t chuyn cc phn ng Ngoi ra gc t do. a. Ruthenium. Trng hp MMA qua ruthenium-xc tc ATRP ln u tin c bo co Sawamoto et al. trong 1995,15 trng hp l thc hin bng cch s dng CCl4 nh khi, RuCl2 complexed 3 equiv ca PPh3 lm cht xc tc, v mt Lewis axit nh methylaluminum bis (2,6-di-tert-butylphenoxide) l hot ha trong 75-80 toluene% 60 C. Trng hp khng c quan st thy trong s vng mt ca axit Lewis. Mt ct truyn tuyn tnh semilogarithmic thi gian chuyn i vs thu c, ch ra mt hng s s16

chui tuyn truyn. Polymer khi lng phn t tng tuyn tnh vi monomer chuyn i ban u nhng lch t l thuyt gi tr chuyn i cao. Chui m rng quan st thy khi b sung cc monomer mi, cho thy trng hp c tnh cht "sng". Cc polyme sn xut monomodal v polydispersities thp (Mw / Mn? 1,3). Kim sot polymerizations sau thu c bng cch s dng RuCl2 (PPh3) 3 / Al (OiPr) 3 l cht xc tc v R-haloesters, chng hn nh ethyl 2-bromoisobutyrate l initiator.164 Trng hp qua trung gian ca hp ruthenium phc tp c xut theo mt con ng cc oan da trn mt s th nghim data.165 Trc tin, trng hp l c ch s hin din ca TEMPO, galvinoxyl, v 1,1-diphenyl-2-picrylhydrazyl (DPPH). Ngc li, s hin din ca H2O hoc methanol khng nh hng n cc phn ng trng hp. Trong thc t, c xc nh r PMMA c thu c thng qua mt h thng treo trng hp trong nc v alcohol.83 th hai, s hin din ca phn na khi xng vo cui-R nhm c xc nhn bng cch phn tch NMR 1H, v chc nng l gn 1. S hin din ca halogen nguyn t nhm cui c xc nhn hai phng php khc nhau: 1H NMR phn tch v sch s m rng chui vi mt ngun cp d liu mi ca MMA s dng mt unisolated v b c lp macroinitiator. Th ba, tacticity ca cc PMMA chun b xc tc ATRP do phc hp ruthenium c mt s thch nh cho syndiotacticity tng t nh chun b bi mt qu trnh gc t do. Cn lu rng intermediacy dai dng Ru (III) cp tin gn y c khng nh trong nghin cu ca ATRP ca MMA bng cch s dng mt Ru binuclear (II) N2-cu ni phc tp, [{RuCl2 (NN N)} 2 (-N2)] (NN N) 2,6-bis (dimethylamino) methyl] pyridin) 0,183 Da trn phn ng ruthenium ATRP cht xc tc carbon s dng phi t trung tm, tc l, 4-isopropyltoluene (P-cymene), 104184185 indenyl (Ind), v cyclopentadienyl (Cp), 159.186 gn y c bo co ( n 13). Mt mi quan h trc tip gia cc arene lability phi t v hot ng ca cht xc tc cho thy rng phi t p-cymene c pht hnh trong qu trnh ATRP. c xc nh polystyrene cng nh PMMA thu c bng cch s dng cc cht xc tc mi vi Mn? 40 000 v Mw / Mn? 1.1. Mt halogen-min ph Ru (II) hydride phc tp, RuH2 (PPh3) 4, cng l nhiu phn ng hn n 12. Molybdat (V) phc hp c s dng nh ATRP cht xc tc 2936 Ha cht, nm 2001, Vol. 101, s 9 Matyjaszewski v Xia Ti v ca Nguyn M vo ngy 30 thng 8 nm 2009 | http://pubs.acs.org Ngy xut bn (Web): Thng Chn 12, 2001 | doi: 10.1021/cr940534g RuCl2 (PPh3) 3. Trng hp ca MMA c th c thc hin ti hoc cao hn nhit phng m khng c s dng ca nhm thm compounds.187 R rng, mt s Ru-n a cht xc tc c th trc tip xc tc cho qu trnh ATRP trong khi ng thi hot ng trong ROMP.188 b. St. Trong s hin din ca mt kim loi preformed phc tp, FeCl2 (PPh3) 2, CCl4 gy ra cc kim sot trng hp ca MMA 80 C trong toluene.116 Cc polymer trng lng phn t tng tuyn tnh vi cc monomer chuyn i ban u, nhng lch t cc gi tr l thuyt c quan st thy cc chuyn i cao hn. Polydispersities c khong 1,4. B sung Al (OiPr) 3 tng tc trng hp, tuy nhin, kim sot trng lng phn t b mt. Cc phn t trng lng gim nh MMA c tiu th vi trng lng phn t polyme thu c mc thp chuyn i. Polydispersity cao (Mw / Mn? 3.0). Mt lot cc halogenua hu c khc, tc l, CHCl2COPh, (CH3) 2CBrCO2Et, v CH3CBr (CO2Et) 2, c s dng nh l khi xng v tr ca CCl4 v dn n cc kim sot trng hp ca MMA vi Mw / Mn) 1,3-1,5. Vi CHCl2COPh hoc (CH3) 2CBrCO2Et khi, khi lng phn t thu c khng tng tuyn tnh vi vic chuyn i monomer v cao hn cc gi tr l thuyt. Khi CH3CBr (CO2Et) 2 c s dng, mt s gia tng tuyn tnh ca cc trng lng phn t chuyn i c quan st thy, tuy nhin, hiu qu khi cn thp. Cc tc gi gn iu ny vi tng tc ca CH3CBr (CO2Et) 2 FeCl2 (PPh3) 2 cht xc tc to thnh mt phc hp st mi. Matyjaszewski et al. bo co trn mt s st ATRP h thng xc tc cho phn ng trng hp kim sot styrene v MMA.98 Nh th hin trong Bng 1, triethyl cht hoa hc, mt phi t ph bin i vi st trong ATRA c hiu qu thp hn trong ATRP. Ngc li, dNbpy, N (NBU) 3, v P (NBU) 3 thc y polymerizations kim sot vi hiu sut khi xng v dn n polyme vi polydispersities thp. T l v polydispersity khc nhau ng k ty thuc vo h thng xc tc s dng cho cc ATRP ca styrene. Khi dNbpy c s dng nh l phi t, trng hp c tin hnh kh chm, monomer chuyn i 64% sau 21 gi 110 C. Polydispersity ca polyme thu c l kh thp (Mw / Mn N3> N2. N1 v vi s lng lin kt C-nguyn t C2> C3. C4. N cng gim R2N? PyrEnDash-> R-Nd> Ph-Nd > Ph-NR- Hot ng thng cao hn cho cu ni v tun hon h thng hn so vi tng t tuyn tnh. V d mt s phi t N-s dng thnh cng trong Cu-ATRP c th hin trong n 17. Phi t c th tham gia pha reactions.207 i vi V d, Kubisa et al. nghin cu ATRP ca mt s acrylates di iu kin khi trng lng phn t thp polyme (Mn) 2000) c nhm mc tiu bng cch s dng tng i nng cao ca cht xc tc. MALDI TOF phn tch cc mu polymer b c lp ti khc nhau giai on ca phn ng trng hp cc tit l rng trong tt nhin ca cc i phn t phn ng trng hp c kh nng hot ng chm dt vi brm dn dn chuyn i thnh cc i phn t hot ng khng c ca thit b u cui brm. Vic chuyn giao dy chuyn c th phi t amin bo c xut. Ngoi ra, amin (v phosphines) phn ng vi alkyl halogenua mt phn ng thay th i nhn, vi mt mt ca HX thng qua mt loi b Hoffman process.208, 209 i vi V d, methyl 2-bromopropionate phn ng vi nbutylamine 25 C trong DMSO vi t l khng i k) 0,0046 M-1 s-1, phn ng vi cc amin i hc chm hn v vi cc amin complexed CuBr lm chm rng n khng th c detected.2092. Photpho phi tu Pht-pho-da trn cc phi t c s dng n phc tp hu ht cc kim loi chuyn tip nghin cu trong ATRP, bao gm c rhenium, 30 ruthenium, 15.104 st, 98.116 rhodium, 43.119 niken, 44.114 v palladium, 118 Tuy nhin, khng ng. PPh3 l cc phi t c s dng thng xuyn nht v c p dng thnh cng phi hp tt c ni trn qu trnh chuyn i kim loi. Mt phi t pht pho, n 17. V d v cc phi t s dng trong ng-trung gian ATRP Atom Chuyn Radical trng hp ha hc Nhn xt, nm 2001, Vol. 101, s 9 nm 2941 Ti v ca Nguyn M vo ngy 30 thng 8 nm 2009 | http://pubs.acs.org Ngy xut bn (Web): Thng Chn 12, 2001 | doi: 10.1021/cr940534g P (NBU) 3, c s dng trong niken v st h thng. Mt lot cc phi t pht pho c nghin cu RuCl2 (p-cymene) loi PR3 catalyst.104 R rng phosphines ch c hai u mnh m c bn v c mt s lng ln steric cng c xc nh (160