Triblock and Pentablock Terpolymers by Sequential Base- Assisted Living Cationic Copolymerization of Functionalized Vinyl Ethers

Transcription

1 Eletroni Supplementry Mteril (ESI) for Polymer Chemistry. This journl is The Royl Soiety of Chemistry 215 Supporting Informtion Trilok nd Pentlok Terpolymers y Sequentil Bse- Assisted Living Ctioni Copolymeriztion of Funtionlized Vinyl Ethers Hssen Bouhékif, Ahlm I Sulmi, Reem D. Alghmdi, Yves Gnnou nd Nikos Hdjihristidis, * King Adullh University of Siene nd Tehnology (KAUST), Thuwl 23955, Kingdom of Sudi Ari Division of Physil Sienes nd Engineering, KAUST Ctlysis Center, Polymer Synthesis L. Division of Physil Sienes nd Engineering. E-mil: (N.H.) nikolos.hdjihristids@kust.edu.s 1

2 Experimentl Setion S1. Generl proedure for the synthesis of monofuntionl (nbea, CEEA Snd idegea) nd difuntionl (HMDEA) inititors S1.1 Synthesis of the nbve-eti id ddut (nbea). This ws prepred y tretment of nbve (9.7(7.51) ml(g),.75mol, p = 94 C) with defult of AOH (2.86(3) ml(g),.5 mol, p = C) t 6 C for 3 h. The rude produt ws distilled twie over lium hydride under redued pressure (6 C) to give nbea (p = 12 C), sweet smelling olorless oil: 75% isolted yield from eti id; purity >99%. 1 H NMR (CDCl 3, ): 5.9 (m,1 H, -OCH(CH 3 )O), 3.7 (m, 1 H, OCHHC), 3.4 (m, 1 H, OCHHC), 2.5 (s,3 H, OCOCH 3 ), 1.55 (m, 1 H, CH 3 CH 2 CH 2 -), 1.4 (d, 2 H, CH 3 CH 2 -), 1.4 (d, 3 H, - OCH(CH 3 )O),.9 (d, 3 H, CH 3 CH 2 -). 13 C NMR (CDCl 3, ): (-OCOCH 3 ), (-OCH(CH 3 )O-), (-OCH 2 CH 2 CH 2 CH 3 ), (-OCH 2 CH 2 CH 2 CH 3 ), (-OCOCH 3 ), 2.99 (-OCH(CH 3 )O-), (-OCH 2 CH 2 CH 2 CH 3 ), 14.1 (-OCH 2 CH 2 CH 2 CH 3 ). The 4 MHz 1 H nd 13 C NMR spetr re shown in Figure S1 in the Supporting Informtion. S1.2 Synthesis of the SiDEGVE-eti id ddut (SiDEGEA). This ws prepred y tretment of SiDEGVE (8(8.6) ml(g), mmol, d = 1.1 g/ml) with n exess of AOH (3(3.148) ml(g), 52.4 mmol, p = C) t 6 C for 8 h. The mixture ws wshed t lest 3 times with wter (1 ml, eh), pre-dried over MgSO 4, nd distilled twie over lium hydride under redued pressure (6 C) to give SiDEGEA (d = 1.1 g/ml), olorless oil: 93% isolted yield from eti id; purity >99%. 1 H NMR (CDCl 3, ): 5.9 (m,1 H, -OCH(CH 3 )O), 3.5 (m, 2 H, -OCH 2 CH 2 OCH 2 CH 2 OSi), (m, 6 H, OCH 2 CH 2 OCH 2 CH 2 OSi), 2 (m, 3 H, -OCOCH 3 ), 1.35 (d, 3 H, CH 3 CH(OCOCH 3 )O-),.84 (s, 12 H, - OSi(CH 3 ) 2 C(CH 3 ) 3 ) nd.3 (s, 6 H, -OSi(CH 3 ) 2 C(CH 3 ) 3 ). 13 C NMR (CDCl 3, ): (-OCOCH 3 ), (-OCH(CH 3 )O-), 72.7 (-OCH 2 CH 2 OCH 2 CH 2 OSi), 7.26 (-OCH 2 CH 2 OCH 2 CH 2 OSi), (- OSi(CH 3 ) 2 C(CH 3 ) 3 ), (-OCOCH 3 ), 2.68 (-OSi(CH 3 ) 2 C(CH 3 ) 3 ), (CH 3 CH(OCOCH 3 )O-) nd - 2

3 5.3 (-OSi(CH 3 ) 2 C(CH 3 ) 3 ). The 4 MHz 1 H nd 13 C NMR spetr re shown in Figure S2 in the Supporting Informtion. S1.3 Synthesis of the CEVE-eti id/ceve (62/38) ddut (CEEA). This ws prepred y tretment of CEVE (5.7(5.95) ml(g), 55.9 mmol, d = 1.48 g/ml, p = 19 C) with n defult of AOH (2(2.98) ml(g), mmol, d = 1.49 g/ml, p = C) t 6 C in 8 h. The rude mteril ws distilled twie over lium hydride under redued pressure (6 C) to give molr rtio of 62/38 CEEA/CEVE, olorless oil with % isolted yield from eti id. 1 H NMR (CDCl 3, ): 5.9 (m,1 H, -OCH(CH 3 )O), 3.9 (m, 2 H, -OCH 2 CH 2 Cl), 3.57 (m, 6 H, OCH 2 CH 2 Cl), 2.4 (m, 3 H, -OCOCH 3 ) nd 1.38 (d, 3 H, CH 3 CH(OCOCH 3 )O-). 13 C NMR (CDCl 3, ): (-OCOCH 3 ), (-OCH(CH 3 )O-), (- OCH 2 CH 2 Cl), (-OCH 2 CH 2 Cl), (-OCOCH 3 ) nd 2.7 (-OCH(CH 3 )O). The 4 MHz 1 H nd 13 C NMR spetr re shown in Figure S3 in the Supporting Informtion. S1.4 Synthesis of HDMEA. This ws prepred y tretment of HDMVE (6.4(5.9) ml(g),.3mol, p = 94 C) with n exess of AOH (5.5(5.76) ml(g),.96 mol, p = C) t 6 C in 3 h. At room temperture, the produt rystllizes. The produt ws then filtered nd then rerystllized twie in diethyl ether t -2 C s white powder. It hd 88% isolted yield from eti id; purity >99%. The produt ws stored t -2 C to prevent its deomposition t room temperture (Figure S4, ESI). 'H NMR (CDCl 3, ): 5.86 (m, 2 H, -OCH(CH 3 )O-), 3.43 nd 3.26 (m, 4 H, eq, CH 3 CH(O-)OCH 2 -), 2.4 (s, 6 H, -OCOCH 3 ), 1.76 nd.93 (m, 8 H, -OCH 2 CH(CH 2 CH 2 -)CH 2 CH 2 -), 1.48 (m, 2 H, -OCH 2 CH(CH 2 - )CH 2 -), 1.36 (d, 6 H, CH 3 CH(O-)O-). 13 C NMR (CDCl 3, ): (2 C, -OCOCH 3 ), 96.5 (2 C, - OCH(CH 3 )O-), 74.7 (2 C, -CH 3 CH(O-)OCH 2 -), 37.9 (2 C, CH 3 CH(O-)OCH 2 CH(CH 2 -)CH 2 -), nd 29.9 (4 C, -OCH 2 CH(CH 2 CH 2 -)CH 2 CH 2 -), 21.3 (2 C, -OCOCH 3 ), 2.7 (2 C, -CH 3 CH(O-)O-). The 4 MHz 1 H nd 13 C NMR spetr re shown in Figure S4 in the Supporting Informtion. 3

4 S2. Monomer synthesis. Synthesis of 2-(tert-Butyldimethylsilyloxy) diethylene glyol vinyl ether (SiDEGVE). A solution of tert-utyldimethylhlorosilne (25g,.17 mol) in N,N-dimethylformmide (DMF; 5 ml) ws dded dropwise to mixture of ethylene glyol monovinyl ether (28.7 ml,.21 mol), imidzole (25 g,.37mol), nd DMF (5 ml) t C under nitrogen. The mixture ws stirred for 6 h t room temperture nd wshed with wter. The rude monomer ws distilled twie over lium hydride under redued pressure; p: 8. C t 1 mmhg. Isolted yield: 8%. Purity: 99% (y gs hromtogrphy). 1 H NMR (CDCl 3, 3 C, ):.5 (s, 6H, -Si(CH 3 ) 2 C(CH 3 ) 3 ),.83 (s, 9H, - Si(CH 3 ) 2 C(CH 3 ) 3 ), 3.56 (m, 4H, -OCH 2 CH 2 OCH 2 CH 2 OSi), 3.71 (m, 2H, -OCH 2 CH 2 OCH 2 CH 2 OSi), 3.75 (m, 2H, OCH 2 CH 2 OCH 2 CH 2 OSi), 3.81 (m, 2H, -OCH 2 CH 2 OCH 2 CH 2 OSi), 3.97 nd 4.15 (m, 2H, H 2 C=), 6.48 (q, 1H,=CH-O-). 13 C NMR (CDCl 3, 3 C, ): (-Si(CH 3 ) 2 C(CH 3 ) 3 ), ((-Si(CH 3 ) 2 C(CH 3 ) 3 ), (-Si(CH 3 ) 2 C(CH 3 ) 3 ), (-OCH 2 CH 2 OCH 2 CH 2 OSi), (-OCH 2 CH 2 OCH 2 CH 2 OSi), (- OCH 2 CH 2 OCH 2 CH 2 OSi), (-OCH 2 CH 2 OCH 2 CH 2 OSi), (m, 2H, H 2 C=), (=CH-O-). The 4 MHz 1 H nd 13 C NMR spetr re shown in Figure S5 in the Supporting Informtion. 4

5 S3. Generl Proedure for the homopolymeriztion of VE monomers using monofuntionl (nbea, CEEA nd SiDEGEA) nd difuntionl (HDMEA) inititors. S3.1 Homopolymeriztion of nbve using the nbea inititor. In the polymeriztion experiments rried out, e.g., in n-hex, with 4 mm of nbea (1 ml,.8 M in n-hex), 2 nd 4 ml of n-bve were respetively dded to ttin n initil onentrtion in nbve of.77 nd 1.56 M, respetively, using either.1(4),.2(8) or.3(12) ml(m) of Al 2 Et 3 Cl 3. The totl volume of the solution ws 2 ml. As n exmple, the results otined t -2 C with [nbve] =.77 M, [nbea] = 4 mm, [DtBP] =.4 mm, [Al 2 Et 3 Cl 3 ] = 4 mm, [AOEt] = 1 M were s follows: 42h = 98%, = 21,4 g/mol, PDI = 1.8 (smple P2.6). For dditionl experimentl dt, see Tles S2 nd S9 in the Supporting Informtion). 1 H NMR in (CDCl 3, ): 3.5 (m, 2 H, -CH 2 CH(OCH 2 -)-), 3 (m, 1 H,-CH 2 CH(O-)-), 1.79 (m, 1 H,- CHHCH(O-)-), 1.5 (m, 1 H,-CHHCH(O-)-), 1.47 (m, 2 H, CH 3 CH 2 CH 2 -), 1.33 (m, 2 H, CH 3 CH 2 -),.87 (d, 3 H, CH 3 CH 2 -). 13 C NMR (CDCl 3, ): 73.9 (-CH 2 CH(O-)-), (-CH 2 CH(OCH 2 -)-), (-CH 2 CH(O-)-), 32.6 (CH 3 CH 2 CH 2 -), 19.7 (CH 3 CH 2 CH 2 -), (CH 3 CH 2 CH 2 -). The 4 MHz 1 H nd 13 C NMR spetr re shown in Figure S7 in the Supporting Informtion. S3.2 Homopolymeriztion of nbve using HDMEA. In the polymeriztion experiments rried out, e.g., in n-hex, with 4 mm of HDMEA (2 ml,.4 M in n-hex), 1, 1.5, 2, 3, 5 nd 8 ml of n-bve were respetively dded to ttin initil onentrtions of nbve(hdmea)(al 2 Et 3 Cl 3 )(Smple) of.38(4)(8)(p8.1),.57(4)(8)(p8.2),.76(4)(8)(p8.3), 1.15(4)(8)(P8.4), 1.92(4)(8)(P8.5), 3.8(4)(8)(P8.6) M(mM)(mM). Here, the polymeriztion ws initited t -2 C y dding.2 ml of Al 2 Et 3 Cl 2 (.8 M in n- Hex). The totl volume of the solution ws 2 ml. As n exmple, the results otined t -2 C for trgeted DP of 77 with [nbve] = 3.8 M, [HDMEA] = 4 mm, [DtBP] =.4 mm, [Al 2 Et 3 Cl 3 ] = 8 mm, [AOEt] = 1 M were s follows: 48h = %, = 8,2 g/mol, PDI = 1.9 (Smple P8.6, ESI). For dditionl experimentl dt, see Tle S8 in the Supporting Informtion. 5

6 S3.3 Homopolymeriztion of SiDEGVE using monofuntionl inititor t -2 C. In the polymeriztion experiments rried out with.8, 1.6, 3 nd 3.9 ml of SiDEGVE using 1 ml of the monofuntionl inititor (i.e., nbea (series P3), SiDEGEA (series P4) or CEEA (series P5)) (.8 M in n-hex),.1 ml of Al 2 Et 3 Cl 3 (.8 M in n-hex) ws respetively dded to ttin n initil onentrtions of SiDEGVE(inititor)(Al 2 Et 3 Cl 3 ) of.16(4)(4),.32(4)(4),.6(4)(4) nd.8(4)(4) M(mM)(mM). The totl volume of the solution ws 2 ml. As n exmple, the results otined t -2 C for [nbve] =.32 M, [nbea] = 4 mm, [DtBP] =.4 mm, [Al 2 Et 3 Cl 3 ] = 4 mm, [AOEt] = 1 M were s follows: x SiDEGVE 384h = 96%, Mn (GPC) = 21,4 g/mol, PDI = 1.14 (Smple P1.2). For dditionl experimentl dt, see Tles S3-S5 nd S1 in the Supporting Informtion. 1 H NMR (CDCl 3, 3 C, ):.3 (s, 6H, -Si(CH 3 ) 2 C(CH 3 ) 3 ),.86 (s, 9H, -Si(CH 3 ) 2 C(CH 3 ) 3 ), 1.5 (m, 1 H,-CHHCH(O-)-), 1.78 (m, 1 H,-CHHCH(O-)-), 3.37 (m, 1 H, -CH 2 CH(O-)-), 3.49 (m, 4H, - OCH 2 CH 2 OCH 2 CH 2 OSi), 3.55 (m, 2H, -OCH 2 CH 2 OCH 2 CH 2 OSi), 3.72 (m, 2H, OCH 2 CH 2 OCH 2 CH 2 OSi). 13 C NMR (CDCl 3, 3 C, ): (-Si(CH 3 ) 2 C(CH 3 ) 3 ), ((- Si(CH 3 ) 2 C(CH 3 ) 3 ), (-Si(CH 3 ) 2 C(CH 3 ) 3 ), (-CH 2 CH(O-)-), (- OCH 2 CH 2 OCH 2 CH 2 OSi), (-OCH 2 CH 2 OCH 2 CH 2 OSi), 7.87 (-OCH 2 CH 2 OCH 2 CH 2 OSi), 72.6 (- OCH 2 CH 2 OCH 2 CH 2 OSi), (-CH 2 CH(O-)-). The 4 MHz 1 H nd 13 C NMR spetr re shown in Figure S9 in the Supporting Informtion. S3.4 Homopolymeriztion of CEVE using nbea t -2 C. The polymeriztion experiments were rried out s desried ove in the generl proedure. In the polymeriztion experiments rried out, e.g., in toluene, with.8 M of CEVE (1.6 ml) nd 1 ml of nbea (.8 M in toluene),.1ml of Al 2 Et 2 Cl 3 (.8 M in n-hex)) ws respetively dded to ttin n initil onentrtion in CEVE(nBEA)(Al 2 Et 3 Cl 3 ) of.8(.4)(.4) M(mM)(M). The totl volume of the solution ws 2 ml. The results otined in toluene t -2 C for [CEVE] =.8 M, [nbea] = 4 mm, [DtBP] =.4 mm, [Al 2 Et 3 Cl 3 ] = 4 mm, 6

7 [AOEt] = 1 M were s follows: x CEVE 312h= 94%, Mn (GPC) = 16,5 g/mol, PDI = 1.34 (Smple P13.6). For dditionl experimentl dt, see Tle S13 in the Supporting Informtion. 1 H NMR (CDCl 3, ): 3.8 (m, 1 H, (ClCH 2 CH 2 O-), 3.72 (m, 1 H, (ClCH 2 CH 2 O-), 3.63 (s, 1 H,-CH 2 CH(O- )-), 1.89 (m, 1 H,-CHHCH(O-)-), 1.67 (m, 1 H,-CHHCH(O-)-). 13 C NMR (CDCl 3, ): (- CH 2 CH(O-)-), (ClCH 2 CH 2 O-), 43.9 (ClCH 2 CH 2 O-), (-CH 2 CH(O-)-). The 4 MHz 1 H nd 13 C NMR spetr re shown in Figure S1 in the Supporting Informtion 7

8 S4. Generl Proedure for the synthesis of the lok polymers y sequentil monomer ddition using the Shlenk tehnique t -2 C. The polymeriztion ws rried out under dry rgon in Shlenk retor equipped with rotflos (ESI, Figure S6) nd mpules ontining monomers for sequentil dditions nd n empty mpule used to remove se smple of the living polymer for moleulr hrteriztion. The retor ws heted under vuum with het gun, ooled down nd trnsferred into gloveox. In typil polymeriztion experiment, e.g. in n-hex, the regents were dded in the min retor in the following order: n-hex (17- x-y-z ml), AOEt (2. ml), monomer (x ml), DtBP (1. ml,.8 M in n-hex) nd inititor (y ml,.4 or.8 M in n-hex). Then p ml of CEVE in n-hex (5% v/v in n-hex) ontining.5p ml of DtBP (.8 M in n-hex) were introdued in mpoule A nd q ml of SiDEGVE in n-hex (5% v/v in hexne) ontining.5p ml of DtBP (.8 M in n-hex) were introdued in mpoule B. The Shlenk retor ws then trnsferred outside the gloveox in ryoth set t -2 C. The polymeriztion ws initited y dding either z =.1y or.2y ml of Al 2 Et 3 Cl 3 (.8 M in n-hex) whether nbea or HDMEA inititor were used s nonfuntionl or difuntionl inititor, respetively. The initil onentrtions were s follows: [nbve] = M, [inititor] = 4-9 mm, [Et 3 Al 2 Cl 3 ] = 4-9 mm, [AOEt] = 1 M nd [DtBP] =.8 mm. After 48h, the CEVE solution ontined in mpoule A ws dded into the min retor through the ridge t -2 C y opening the rotflo (A). After 12 h, n liquot ws tken from mpoule C to hek t x CEVE 12h= % the moleulr dimension of the PnBVE--PCEVE dilok prior to the ddition t -2 C y opening the rotflo (B) of the SiDEGVE solution ontined in mpoule B. After given time, the polymeriztion ws quenhed with mmonil methnol (3% v/v). The quenhed retion mixtures were sequentilly wshed with diluted hydrohlori id nd with wter to remove the tlyst residues. The n-hex smple ontining the polymer, i.e., PnBVE--PCEVE--PSiDEGVE, ws then dried over MgSO 4, evported to dryness under redued pressure, nd vuum dried overnight to give the produt polymers. The onversion of the monomer ws mesured y grvimetry of the produt. 8

9 S4.1 Synthesis of the PnBVE--PCEVE t -2 C. The polymeriztion experiments were rried out s desried ove in the generl proedure. n-hex (14.9 ml), AOEt (2. ml), nbve (1. ml), DtBP (1. ml,.8 M in n-hex), nbea (1. ml,.8 M in n-hex) nd Al 2 Et 3 Cl 3 (.1 ml,.8 M in n-hex) were used t -2 C for trgeting DP of ; 48h = %, Mn (GPC) (PDI)(smple) = 9,8(1.8)(P7.1), 1,5(1.7)(P3) nd 1,2(1.8)(P31) g/mol. After 48 h, 2()()(P7.5), 1()(1)(P3) nd.2(.8)(1.)(p31) ml(ml)(ml) of CEVE(nBVE)(n-Hex)(series) were dded to living PnBVE tions of the solution for the preprtion of PnBVE --PCEVE 2, PnBVE --PCEVE 7 nd PnBVE P(nBVE.8 -o-ceve.2 ) 7, respetively. As n exmple, the results otined for the synthesis of PnBVE --PCEVE 7 were s follows: x CEVE 72h = 61%, = 18, g/mol, PDI = 1,9 (Smple P3, Tle 1). The 4 MHz 1 H nd 13 C NMR spetr of P3 nd P31 re shown in Figures S11 nd S12 in the Supporting Informtion. S4.2 Synthesis of the PnBVE--PSiEGVE t -2 C. The polymeriztion experiments were rried out s desried ove in the generl proedure. n-hex (14.9 ml), AOEt (2. ml), nbve (1. ml), DtBP (1. ml,.8 M in n-hex), nbea (1. ml,.9 M in n-hex) nd Al 2 Et 3 Cl 3 (.1 ml,.8 M in n-hex) were used t -2 C for trgeting DP of 84; t( t )(Mn (GPC) )(PDI)(smple) = 42(96)(8,6)(1.8)(P32) nd 48()(8,4)(1.7)(P33) h (Tle 1). After 42 nd 48h, 2.6 ml of SiEGVE (5% v/v in n- Hex) ws dded to living PnBVE tions of the solution for the preprtion of PnBVE 85 --PSiEGVE 6 nd PnBVE 85 --PSiEGVE 62, respetively; x SiDEGVE 72h ( )(PDI)(smple) = 82(21,4)(1.19)(P32) nd (85)(23,8)(1.1)(P33) % (Tle 1). The 4 MHz 1 H nd 13 C NMR spetr re shown in Figure S13 in the Supporting Informtion. S4.3 Synthesis of the PnBVE--PCEVE--PSiEGVE t -2 C. The polymeriztion experiments were rried out s desried ove in the generl proedure using the stok solution nbea1 (.9 M in n- Hex), nbea2 (.8 M in n-hex), DtBP (.8 M in n-hex) nd Al 2 Et 3 Cl 3 (.8 M in n-hex). In the polymeriztion experiments rried out with 4 nd 9 mm of nbea, 12.6(2)(2)(2)()(1)(.4)(P34) nd 9

10 13.8(2)(2)()(1)(1)(.2)(P35) ml(ml)(ml)(ml)(ml)(ml) of nhex(nbve)(aoet)(nbea1)(nbea2)(dtbp)(al 2 Et 3 Cl 3 )(smple) were used to prepre living PnBVE tions of DP 88 nd 2, respetively; 48h = %, Mn (GPC) (PDI)(series) = 8,8(1.8)(P34) nd 2,(1.9)(P35) g/mol. After 48 h, PnBVE 9 --PCEVE 98 nd PnBVE 2 --PCEVE 216 were prepred y the ddition of 3.4 ml of CEVE (5% v/v in n-hex) ontining of DtBP (.1 ml,.8m in n- Hex) on living PnBVE tions; x CEVE 12h = %, Mn (GPC) (PDI)(series) = 17,8(1.17)(P34) nd 43,2(1.18)(P35) g/mol. After 12 h, 4 ml of SiEGVE (5 % v/v in nhx) were dded to the living PnBVE 9 --PCEVE 98 tions nd 7.6 ml of SiEGVE (5 % v/v in nhx) were dded to PnBVE 2 -- PCEVE 216 tions, to otin t -2 C PnBVE 9 --PCEVE 98 --PSieGVE 24 (P34) nd PnBVE 2 -- PCEVE PSieGVE 192 (S34), respetively; x SiEGVE t (time)(mn (GPC) )(PDI)(series) = (6)(12)(23,8)(1.17)(P34) nd (24)(9,6)(1.18)(P35) %(h). For dditionl experimentl dt, see Tle 1 nd Tles S33-34 in the Supporting Informtion. The 4 MHz 1 H nd 13 C NMR spetr of P34 nd P35 re shown in Figure S14 nd S15 in the Supporting Informtion. S4.4 Synthesis of the PCEVE--PnBVE--PCEVE t -2 C. The polymeriztion experiments were rried out s desried ove in the generl proedure. In the polymeriztion experiments rried out with 4 mm of HDMEA (2 ml,.4 M in n-hex) nd x = 2 nd 5.2 ml of nbve, n-hex (14.8-x ml), AOEt (2. ml), DtBP (1. ml,.8 M in n-hex) nd Al 2 Et 3 Cl 3 (.2 ml,.8 M in n-hex) were used t -2 C for trget DP of 2 nd 5, respetively; (time)(mn (GPC) )(PDI)(series) = (42)(21,)(1.6)(P36), (48)(55,)(1.7)(P37) nd (48)(53,2)(1.7)(P38) %(h). After 48 h, 3.4 ml of CEVE (5%v/v in n-hex) ontining of DtBP (.1mL,.8M in n-hx) were dded to living, -PnBVE tions for the preprtion of PCEVE 82 --PnBVE 2 --PCEVE 82 (P36) nd PCEVE 98 --PnBVE 5 --PCEVE 98 (P37), respetively. Similrly, PCEVE 2 -lok-pnbve 5 --PCEVE 2 (P38) ws prepred using.4 ml of CEVE (5% v/v in nhex). The results otined for the synthesis of PCEVE 82 --PnBVE 2 --PCEVE 82, PCEVE 98 --PnBVE 5 --PCEVE 98 nd PCEVE 2 --PnBVE

11 PCEVE 2 were s follows: x CEVE (time)( )(PDI)(smple) = 81(72)(38,7)(1.2)(P36), (12)(75,7)(1.9)(P37) nd (12)(57,)(1.9)(P38) %. For dditionl experimentl dt, see Tle 2. The 4 MHz 1 H nd 13 C NMR spetr of P36, P37 nd P38 re shown in Figures S16- S18 in the Supporting Informtion. S4.5 Synthesis of the PSiEGVE--PnBVE--PSiEGVE t -2 C. The polymeriztion experiments were rried out s desried ove in the generl proedure. In the polymeriztion experiments rried out with 4 mm of HDMEA (2 ml,.4 M in n-hex) nd x = 2 nd 5.2 ml of nbve, n-hex (14.8-x ml), AOEt (2. ml), DtBP (1. ml,.8 M in n-hex) nd Al 2 Et 3 Cl 3 (.2 ml,.8 M in n-hex) were used t -2 C to trget DP of 2 nd 5, respetively; (time)(mn (GPC) )(PDI)(smple) = 97(42)(21,2)(1.6)(P39), (48)(54,8)(1.6)(P4) (48)(52,3)(1.6)(P41). After 48 h, 8 nd 1 ml of SiEGVE (5% v/v in n-hex) ontining of DtBP (.1mL,.8M in n-hx) were dded to living PnBVE 5 tions for the preprtion of PSiEGVE 11 --PnBVE 5 --PSiEGVE 11 (P39) nd PSiEGVE 1 - -PnBVE 5 --PSiEGVE 1 (P4), respetively. Similrly, PSiEGVE 37 --PnBVE 2 --PSiEGVE 37 (P41) ws prepred using 3 ml of SieGVE (5% v/v in nhex). The results otined for the synthesis of PSiEGVE 11 --PnBVE 5 --PSiEGVE 11, PSiEGVE 1 --PnBVE 5 --PSiEGVE 1 nd PSiDEGVE PnBVE 2 --PSiDEGVE 37 re x SiDEGVE time (time)( )(PDI)(series) = 75(12)(38,2)(1.15)(P39), (384)(15,6)(1.12)(P4) nd (384)(58,)(1.9)(P41) %(h). For dditionl experimentl dt, see Tle 2 nd Tles S39-S41 in the Supporting Informtion. The 4 MHz 1 H nd 13 C NMR spetr of P39, P4 nd P41 re shown in Figures S19-S21 in the Supporting Informtion. S4.6 Synthesis of the PSiEGVE--PCEVE--PnBVE--PCEVE--PSiEGVE t -2 C. The polymeriztion experiments were rried out s desried ove in the generl proedure. In the polymeriztion experiments rried out with 4 mm of HDMEA (2. ml,.4 M in n-hex), n-hex (14.8- x ml), nbve (x=5.2 ml), AOEt (2. ml), DtBP (1. ml,.8 M in n-hex) nd Al 2 Et 3 Cl 3 (.2 ml,.8 M in n-hex) were used t -2 C for trget DP of 5; = 53, g/mol, PDI = 1.8 nd yield = 11

12 % (P42). After 48 h, 3.4 ml of CEVE (5% v/v in n-hex) ontining DtBP (.1mL,.8M in n-hx) were dded to living PnBVE tions for the preprtion of PCEVE 97 --PnBVE 5 --PCEVE 97 ; x CEVE 12h = %, = 73,2 g/mol, PDI = 1.9 (P42). After 12 h, 4 ml of SiEGVE (5 % v/v in n- Hex) were used t -2 C to otined the PSiEGVE --PCEVE 97 --PnBVE 5 --PCEVE PSiEGVE ; x SiDEGVE 384h = %, = 98,4 g/mol, PDI = 1.14 (smple P42). For dditionl experimentl dt, see Tle 2 nd Tle S41 in the Supporting Informtion. The 4 MHz 1 H nd 13 C NMR spetr of P42 re shown in Figure S22 in the Supporting Informtion. 12

13 1 H NMR (CDCl 3, ): 5.9 (m,1 H, -OCH(CH 3 )O), 3.7 (m, 1 H, OCHHC), 3.4 (m, 1 H, OCHHC), 2.5 (s,3 H, OCOCH 3 ), 1.55 (m, 1 H, CH 3 CH 2 CH 2 -), 1.4 (d, 2 H, CH 3 CH 2 -), 1.4 (d, 3 H, -OCH(CH 3 )O),.9 (d, 3 H, CH 3 CH 2 -). Fig S1: 4 MHz 1 H NMR spetrum of nbve-aeti Aid Addut (nbea). 13 C NMR (CDCl 3, ): (-OCOCH 3 ), (-OCH(CH 3 )O-), (-OCH 2 CH 2 CH 2 CH 3 ), (-OCH 2 CH 2 CH 2 CH 3 ), (-OCOCH 3 ), 2.99 (-OCH(CH 3 )O-), (-OCH 2 CH 2 CH 2 CH 3 ), 14.1 (-OCH 2 CH 2 CH 2 CH 3 ). Figure S1: 4 MHz 13 C NMR spetrum of nbve-aeti Aid Addut (nbea) 13

14 8E+5 7E+5 6E+5 6E+5 6E+5 5E+5 4E+5 4E+5 4E+5 3E+5 2E+5 2E+5 2E+5 1E f1 (ppm) H NMR (CDCl 3, ): 5.9 (m,1 H, -OCH(CH 3 )O), 3.5 (m, 2 H, -OCH 2 CH 2 OCH 2 CH 2 OSi), (m, 6 H, OCH 2 CH 2 OCH 2 CH 2 OSi), 2 (m, 3 H, -OCOCH 3 ), 1.35 (d, 3 H, CH 3 CH(OCOCH 3 )O-),.84 (s, 12 H, -OSi(CH 3 ) 2 C(CH 3 ) 3 ) nd.3 (s, 6 H, -OSi(CH 3 ) 2 C(CH 3 ) 3 ). Fig. S2: 4 MHz 1 H NMR spetrum of tbdmsiegve-aeti Aid Addut (tbdmsiegea) f1 (ppm) C NMR (CDCl 3, ): (-OCOCH 3 ), (-OCH(CH 3 )O-), 72.7 (-OCH 2 CH 2 OCH 2 CH 2 OSi), 7.26 (-OCH 2 CH 2 OCH 2 CH 2 OSi), (- OSi(CH 3 ) 2 C(CH 3 ) 3 ), (-OCOCH 3 ), 2.68 (-OSi(CH 3 ) 2 C(CH 3 ) 3 ), (CH 3 CH(OCOCH 3 )O-) nd (-OSi(CH 3 ) 2 C(CH 3 ) 3 ). Fig. S2: 4 MHz 13 C NMR spetrum of tbdmsiegve -Aeti Aid Addut (tbdmsiegea). 14

15 E+5 6E+5 6E+5 5E+5 4E+5 4E+5 4E+5 3E+5 2E+5 2E+5 2E+5 1E E f1 (ppm) H NMR (CDCl 3, ): 5.9 (m,1 H, -OCH(CH 3 )O), 3.9 (m, 2 H, -OCH 2 CH 2 Cl), 3.57 (m, 6 H, OCH 2 CH 2 Cl), 2.4 (m, 3 H, -OCOCH 3 ) nd 1.38 (d, 3 H, CH 3 CH(OCOCH 3 )O-). Fig. S3: 4 MHz 1 H NMR spetrum of CEVE-Aeti Aid/CEVE (62/38) Addut (CEEA) f1 (ppm) C NMR (CDCl 3, ): (-OCOCH 3 ), (-OCH(CH 3 )O-), (-OCH 2 CH 2 Cl), (-OCH 2 CH 2 Cl), (-OCOCH 3 ) nd 2.7 (- OCH(CH 3 )O). Fig. 3: 4 MHz 13 C NMR spetrum of CEVE-Aeti Aid/CEVE (62/38) Addut (CEEA). 15

16 ppm 'H NMR (CDCl 3, ): 5.86 (m, 2 H, -OCH(CH 3 )O-), 3.43 nd 3.26 (m, 4 H, eq, CH 3 CH(O-)OCH 2 -), 2.4 (s, 6 H, -OCOCH 3 ), 1.76 nd.93 (m, 8 H, -OCH 2 CH(CH 2 CH 2 -)CH 2 CH 2 -), 1.48 (m, 2 H, -OCH 2 CH(CH 2 -)CH 2 -), 1.36 (d, 6 H, CH 3 CH(O-)O-). Fig. S4: 4 MHz 1H NMR spetrum of HMDEA ppm C NMR (CDCl 3, ): (2 C, -OCOCH 3 ), 96.5 (2 C, -OCH(CH 3 )O-), 74.7 (2 C, -CH 3 CH(O-)OCH 2 -), 37.9 (2 C, CH 3 CH(O-)OCH 2 CH(CH 2 - )CH 2 -), nd 29.9 (4 C, -OCH 2 CH(CH 2 CH 2 -)CH 2 CH 2 -), 21.3 (2 C, -OCOCH 3 ), 2.7 (2 C, -CH 3 CH(O-)O-). Fig. S4: 4 MHz 13 C NMR spetrum of HMDEA. 16

17 O O O O O O Purity > 99.7% HO O O OH Extrted impurities O O Figure S4: 4 MHz 13 C NMR spetrum of HMDEA fter rerystlliztion (purity > 99.7%). 1 H NMR (CDCl 3, 3 C, ):.5 (s, 6H, -Si(CH 3 ) 2 C(CH 3 ) 3 ),.83 (s, 9H, -Si(CH 3 ) 2 C(CH 3 ) 3 ), 3.56 (m, 4H, -OCH 2 CH 2 OCH 2 CH 2 OSi), 3.71 (m, 2H, -OCH 2 CH 2 OCH 2 CH 2 OSi), 3.75 (m, 2H, OCH 2 CH 2 OCH 2 CH 2 OSi), 3.81 (m, 2H, -OCH 2 CH 2 OCH 2 CH 2 OSi), 3.97 nd 4.15 (m, 2H, H 2 C=), 6.48 (q, 1H,=CH-O-). Fig. S5: 4 MHz 1 H NMR spetrum of tbdmsiegve. 17

18 13 C NMR (CDCl 3, 3 C, ): (-Si(CH 3 ) 2 C(CH 3 ) 3 ), ((-Si(CH 3 ) 2 C(CH 3 ) 3 ), (-Si(CH 3 ) 2 C(CH 3 ) 3 ), (-OCH 2 CH 2 OCH 2 CH 2 OSi), (-OCH 2 CH 2 OCH 2 CH 2 OSi), (-OCH 2 CH 2 OCH 2 CH 2 OSi), (-OCH 2 CH 2 OCH 2 CH 2 OSi), (m, 2H, H 2 C=), (=CH-O-). Fig. S5: 4 MHz 13 C NMR spetrum of tbdmsiegve 18

19 E+6 9E+5 8E+5 7E+5 6E+5 5E+5 4E+5 3E+5 2E+5 1E+5-1E E ppm H NMR in (CDCl 3, ): 3.5 (m, 2 H, -CH 2 CH(OCH 2 -)-), 3 (m, 1 H,-CH 2 CH(O-)-), 1.79 (m, 1 H,-CHHCH(O-)-), 1.5 (m, 1 H,-CHHCH(O-)-), 1.47 (m, 2 H, CH 3 CH 2 CH 2 -), 1.33 (m, 2 H, CH 3 CH 2 -),.87 (d, 3 H, CH 3 CH 2 -). Fig. S7: 4 MHz 1 H NMR spetrum of PnBVE in CDCl f1 (ppm) C NMR (CDCl 3, ): 73.9 (-CH 2 CH(O-)-), (-CH 2 CH(OCH 2 -)-), (-CH 2 CH(O-)-), 32.6 (CH 3 CH 2 CH 2 -), 19.7 (CH 3 CH 2 CH 2 -), (CH 3 CH 2 CH 2 -). Fig. S7: 4 MHz 13 C NMR spetrum of rude PnBVE in CDCl 3 19

20 E+5 7E+5 6E+5 6E+5 6E+5 5E+5 4E+5 4E+5 4E+5 3E+5 2E+5 2E+5 2E+5 1E ppm H NMR (CDCl 3, 3 C, ):.3 (s, 6H, -Si(CH 3 ) 2 C(CH 3 ) 3 ),.86 (s, 9H, -Si(CH 3 ) 2 C(CH 3 ) 3 ), 1.5 (m, 1 H,-CHHCH(O-)-), 1.78 (m, 1 H,- CHHCH(O-)-), 3.37 (m, 1 H, -CH 2 CH(O-)-), 3.49 (m, 4H, -OCH 2 CH 2 OCH 2 CH 2 OSi), 3.55 (m, 2H, -OCH 2 CH 2 OCH 2 CH 2 OSi), 3.72 (m, 2H, OCH 2 CH 2 OCH 2 CH 2 OSi). Fig. S9: 4 MHz 1 H NMR spetrum of PSiDEGVE in CDCl ppm C NMR (CDCl 3, 3 C, ): (-Si(CH 3 ) 2 C(CH 3 ) 3 ), ((-Si(CH 3 ) 2 C(CH 3 ) 3 ), (-Si(CH 3 ) 2 C(CH 3 ) 3 ), (-CH 2 CH(O-)-), (-OCH 2 CH 2 OCH 2 CH 2 OSi), (-OCH 2 CH 2 OCH 2 CH 2 OSi), 7.87 (-OCH 2 CH 2 OCH 2 CH 2 OSi), 72.6 (-OCH 2 CH 2 OCH 2 CH 2 OSi), (- CH 2 CH(O-)-). Fig. S9: 4 MHz 13 C NMR spetrum of PSiDEGVE in CDCl 3 2

21 E+5 6E+5 6E+5 6E+5 5E+5 4E+5 4E+5 4E+5 3E+5 2E+5 2E+5 2E+5 1E E f1 (ppm) H NMR (CDCl 3, ): 3.8 (m, 1 H, (ClCH 2 CH 2 O-), 3.72 (m, 1 H, (ClCH 2 CH 2 O-), 3.63 (s, 1 H,-CH 2 CH(O-)-), 1.89 (m, 1 H,-CHHCH(O-)-), 1.67 (m, 1 H,-CHHCH(O-)-). Fig. S1: 4 MHz 1 H NMR spetrum of rude PCEVE in CDCl f1 (ppm) C NMR (CDCl 3, ): (-CH 2 CH(O-)-), (ClCH 2 CH 2 O-), 43.9 (ClCH 2 CH 2 O-), (-CH 2 CH(O-)-). Fig. S1: 4 MHz 1 H NMR spetrum of rude PCEVE in CDCl 3 21

22 Fig. 6. Shlenk retors used for the synthesis t -2 C in n-hexne of triloks ABC nd pentloks CBABC terpolymers y living tioni polymeriztion of vinyl ether y sequentil monomer ddition. Figure 6. Shlenk retors, equipped with smpling mpoule, used for the synthesis of lok triloks ABC nd pentloks CBABC terpolymers y living tioni polymeriztion of vinyl ether monomer y sequentil monomer ddition. 22

23 Tle S1: Results from the polymeriztion of nbve initited y 1/2 n/n HMDEA/Al 2 Et 3 Cl 3 in the presene of 2,6-di tert utylpyridine (DtBP) in n-hex t -2 C. [nbve] = 2 M, [AOEt] = 1 M, [HMDEA] = 4 mm, [Al 2 Et 3 Cl 3 ] = 8 mm nd [DtBP] =.4 mm. Series P1.1 P1.2 P1.3 P1.4 P1.5 P1.6 Time (h) 1h4mn 3h2mn 5h 7h 28h 32h xtime VE ,11 19,53 24,4 29,3 48,7 5, 8,78 21, 26,3 31,6 54,4 55, PDI The frtion of the VE monomer onverted into polymer ws mesured y grvimetry of the produt. Mnth = [nbve] /[HMDEA] xtime VE.16 g/mol The verge numer moleulr weight (Mn(GPC) ) nd moleulr weight distriution (M w /M n ) were determined y GPC in THF ginst PS stndrds Tle S2: Results from the polymeriztion of nbve initited y 1/1 n/n nbea/al 2 Et 3 Cl 3 in the presene of 2,6 di tert utylpyridine (DtBP) in n-hex t -2 C. [nbve] =.77 M, [AOEt] = 1 M, [nbea] = 4 mm, [Al 2 Et 3 Cl 3 ] = 4 mm nd [DtBP] =.4 mm. Series P2.1 P2.2 P2.3 P2.4 P2.5 P2.6 Time (h) 6h45mn 1h 11h1 12h45 2h4 41h15 time ,9 1,4 11,2 12, 15,4 18,5 8,22 1,72 11,4 12, 18, 21,4 PDI The frtion of the VE monomer onverted into polymer ws mesured y grvimetry of the produt. Mnth = [nbve] /[nbea] time.16 g/mol The verge numer moleulr weight (Mn(GPC) ) nd moleulr weight distriution (M w /M n ) were determined y GPC in THF ginst PS stndrds 23

24 Tle S3: Results from the polymeriztion of SiDEGVE initited y 1/1 n/n nbea/al 2 Et 3 Cl 3 in the presene of 2,6-di-tert utylpyridine (DtBP) in n-hex t -2 C. [SiDEGVE] =.32 M, [AOEt] = 1 M, [nbea] = 4 mm, [Al 2 Et 3 Cl 3 ] = 4 mm nd [DtBP] =.4 mm. Series Time (h) x SiDEGVE time PDI P3.1 P3.2 P3.3 P3.4 P ,16 5,94 12,28 17,23 18,82 4,5 6,2 13, 17,5 19, The frtion of the VE monomer onverted into polymer ws mesured y grvimetry of the produt. Mnth = [SiDEGVE] /[nbea] x SiDEGVE time g/mol The verge numer moleulr weight (Mn(GPC) ) nd moleulr weight distriution (M w /M n ) were determined y GPC in THF ginst PS stndrds Tle S4: Results from the polymeriztion of SiDEGVE initited y 1/1 n/n SiDEGEA/Al 2 Et 3 Cl 3 in the presene of 2,6 di tert utylpyridine (DtBP) in n-hex t -2 C. [SiDEGVE] =.32 M, [AOEt] = 1 M, [SiDEGEA] = 4 mm, [Al 2 Et 3 Cl 3 ] = 4 mm nd [DtBP] =.4 mm. Series P4.1 P4.2 P4.3 P4.4 P4.5 P4.6 Time (h) x SiDEGVE time ,98 3,35 5,4 14,9 19, 19,8 2,5 3,8 5,7 15, 19,2 2,5 PDI The frtion of the VE monomer onverted into polymer ws mesured y grvimetry of the produt. Mnth = [SiDEGVE] /[SiDEGEA] x SiDEGVE time g/mol The verge numer moleulr weight (Mn(GPC) ) nd moleulr weight distriution (M w /M n ) were determined y GPC in THF ginst PS stndrds 24

25 Tle S5: Results from the homopolymeriztion of SiDEGVE initited y 1/1 n/n nceea/al 2 Et 3 Cl 3 in the presene of 2,6-di tert utylpyridine (DtBP) in n-hex t -2 C. [SiDEGVE] =.32 M, [AOEt] = 1 M, [nbea] = 4 mm, [Al 2 Et 3 Cl 3 ] = 4 mm nd [DtBP] =.4 mm. Series Time (h) x SiDEGVE time PDI P5.1 P5.2 P5.3 P ,32 13,42 18,62 19,8 9, 14,3 2, 22, The frtion of the VE monomer onverted into polymer ws mesured y grvimetry of the produt. Mnth = [SiDEGVE] /[CEEA] x SiDEGVE time g/mol The verge numer moleulr weight (Mn(GPC) ) nd moleulr weight distriution (M w /M n ) were determined y GPC in THF ginst PS stndrds Tle S6: Results from the homopolymeriztion of CEVE initited y 1/1 n/n PnBVE 95 +/Al 2 Et 3 Cl 3 in the presene of 2,6-di tert utylpyridine (DtBP) in n-hex t -2 C. [CEVE] =.32 M, [AOEt] = 1 M, [PnBVE 95 +] = 4 mm, [Al 2 Et 3 Cl 3 ] = 4 mm nd [DtBP] =.4 mm. Time of polymeriztion of t=12h. Series P7. d P6.1 P6.2 P6.3 P6.4 Time (h) x CEVE time N.A. 16,5 19,7 23,67 28,2 9,5 16,9 2,3 24,5 29, PDI The frtion of the VE monomer onverted into polymer ws mesured y grvimetry of the produt. Mnth = [CEVE] /[PnBVE 95 +] x CEVE 12h 16.2 g/mol The verge numer moleulr weight (Mn(GPC) ) nd moleulr weight distriution (M w /M n ) were determined y GPC in THF ginst PS stndrds d Experimentl onditions : Living PnBVE tion ([nbve] =.87 M, [nbea] = [Al 2 Et 3 Cl 3 ] = 4.34 mm), [AOEt] = 1.9 M [DtBP] =.44 mm, V T = 18.4 ml, 42h = %, Mn (GPC) = 9,5 g/mol; PDI = 1.8) 25

26 Tle S8: Results from the dependene of nd M w(gpc) /M n(gpc vs [nbve] /[HMDEA] x 46h, from the homopolymeriztion of nbve initited y 1/2 n/n nbea/al 2 Et 3 Cl 3 in the presene of 2,6-di-tert utylpyridine (DtBP) in n-hex t -2 C. [nbve] = M, [AOEt] = 1 M, [HMDEA] = 4 mm, [Al 2 Et 3 Cl 3 ] = 8 mm nd [DtBP] =.4 mm. Time of polymeriztion of t=46h. Series [nbve] Trgeted DP P8.1 P8.2 P8.3 P8.4 P8.5 P h 9,27 14,46 19,25 28,9 46,2 77, 8,9 14,8 23,2 29,8 46,5 81,7 The frtion of the VE monomer onverted into polymer ws mesured y grvimetry of the produt. Mnth = [nbve] /[HMDEA] 46h.16 g/mol The verge numer moleulr weight (Mn(GPC) ) nd moleulr weight distriution (M w /M n ) were determined y GPC in THF ginst PS stndrds PDI Tle S9: Results from the dependene of nd M w(gpc) /M n(gpc vs [nbve] /[nbea] x 46h, from the homopolymeriztion of nbve initited y 1/1 n/n nbea/al 2 Et 3 Cl 3 in the presene of 2,6-di-tert utylpyridine (DtBP) in n-hex t -2 C. [nbve] = M, [AOEt] = 1 M, [nbea] = 4 mm, [Al 2 Et 3 Cl 3 ] = 4 mm nd [DtBP] =.4 mm. Time of polymeriztion of t=46h. Series [nbve] Trgeted DP 46h PDI 26

27 P9.1 P9.2 P9.3 P ,5 19,5 39, 78, 1, 19,5 41,6 8, The frtion of the VE monomer onverted into polymer ws mesured y grvimetry of the produt. Mnth = [nbve] /[nbea] 46h.16 g/mol The verge numer moleulr weight (Mn(GPC) ) nd moleulr weight distriution (M w /M n ) were determined y GPC in THF ginst PS stndrds Tle S1: Results from the dependene of nd M w(gpc) /M n(gpc vs [SiDEGVE] /[nbea] x x SiDEGVE 42h, from the homopolymeriztion of SiDEGVE initited y 1/1 n/n nbea/al 2 Et 3 Cl 3 in the presene of 2,6-di-tert-utylpyridine (DtBP) in n-hex t -2 C. [SiDEGVE] = M, [AOEt] = 1 M, [nbea] = 4 mm, [Al 2 Et 3 Cl 3 ] = 4 mm nd [DtBP] =.4 mm. Time of polymeriztion of t=42h. Series [SiDEGVE] Trgeted DP x SiDEVE 42h PDI P1.1 P1.2 P1.3 P ,3 24,6 36,97 49,3 11,5 21,4 39, 47, The frtion of the VE monomer onverted into polymer ws mesured y grvimetry of the produt. Mnth = [SiDEGVE] /[nbea] x SiDEGVE 42h g/mol The verge numer moleulr weight (Mn(GPC) ) nd moleulr weight distriution (M w /M n ) were determined y GPC in THF ginst PS stndrds Tle S11: Results from the dependene nd M w(gpc) /M n(gpc vs [CEVE] /[PnBVE 95 +] x x CEVE 12h, from the homopolymeriztion of CEVE initited y 1/1 n/n PnBVE 95 +/Al 2 Et 3 Cl 3 in the presene of 2,6-di-tert utylpyridine (DtBP) in n-hex t -2 C. [CEVE] = M, [AOEt] = 1 M, [PnBVE+] = 4 mm, [Al 2 Et 3 Cl 3 ] = 4 mm nd [DtBP] =.4 mm. Time of polymeriztion of t=12h. Series [CEVE] Trgeted DP x CEVE 12h PDI 27

28 P7. d P11.1 P11.2 P11.3 P N.A. 99 N.A. 14,8 2, 3,7 4,3 9,5 14,2 2, 3,2 36, The frtion of the VE monomer onverted into polymer ws mesured y grvimetry of the produt. Mnth = [CEVE] /[nbea] x CEVE 12h g/mol The verge numer moleulr weight (Mn(GPC) ) nd moleulr weight distriution (M w /M n ) were determined y GPC in THF ginst PS stndrds d Experimentl onditions : Living PnBVE tion ([nbve] =.87 M, [nbea] = [Al 2 Et 3 Cl 3 ] = 4.34 mm), [AOEt] = 1.9 M [DtBP] =.44 mm, V T = 18.4 ml, 42h = %, Mn (GPC) = 9,5 g/mol; PDI = 1.8) Tle S12: Results from the homopolymeriztion of nbve initited y 1/1 n/n nbea/al 2 Et 3 Cl 3 in the presene of 2,6-di-tert-utylpyridine (DtBP) in toluene t -2 C. [nbve] =.77 M, [AOEt] = 1 M, [nbea] = 4 mm, [Al 2 Et 3 Cl 3 ] = 4 mm nd [DtBP] =.4 mm. Series P12.1 P12.2 P12.3 P12.4 P12.5 P12.6 P12.7 P12.8 P12.9 P12.1 Time (h) time ,2 11,76 12,73 13,5 15,81 17,35 18,32 18,7 19,28 19,28 1,3 12,2 12,6 13, 15,6 19, 22, 23, 24,5 26,8 PDI The frtion of the VE monomer onverted into polymer ws mesured y grvimetry of the produt. Mnth = [nbve] /[nbea] time.16 g/mol The verge numer moleulr weight (Mn(GPC) ) nd moleulr weight distriution (M w /M n ) were determined y GPC in THF ginst PS stndrds Tle S13: Results from the homopolymeriztion of CEVE initited y 1/1 n/n nbea/al 2 Et 3 Cl 3 in the presene of 2,6-di-tert-utylpyridine (DtBP) in toluene t -2 C. [CEVE] =.8 M, [AOEt] = 1 M, [nbea] = 4 mm, [Al 2 Et 3 Cl 3 ] = 4 mm nd [DtBP] =.4 mm. 28

29 Series Time (h) time PDI P13.1 P13.2 P13.3 P13.4 P13.5 P ,9 5,9 9, 1,6 12,7 19,9 1,3 4,4 6,9 8, 9,3 2, The frtion of the VE monomer onverted into polymer ws mesured y grvimetry of the produt. Mnth = [CEVE] /[nbea] x CEVE time 16.2 g/mol The verge numer moleulr weight (Mn(GPC) ) nd moleulr weight distriution (M w /M n ) were determined y GPC in THF ginst PS stndrds Tle S14: Results from the homopolymeriztion of SiDEGVE initited y 1/1 n/n nbea/al 2 Et 3 Cl 3 in the presene of 2,6-di-tert-utylpyridine (DtBP) in toluene t -2 C. [SiDEGVE] =.32 M, [AOEt] = 1 M, [nbea] = 4 mm, [Al 2 Et 3 Cl 3 ] = 4 mm nd [DtBP] =.4 mm. Series Time (h) x SiDEGVE time PDI P14.1 P14.2 P14.3 P14.4 P14.5 P ,14 1,6 11,4 12,6 16,16 18,9 6,3 1,8 11,3 14, 14,4 2, The frtion of the VE monomer onverted into polymer ws mesured y grvimetry of the produt. Mnth = [nbve] /[nbea] time g/mol The verge numer moleulr weight (Mn(GPC) ) nd moleulr weight distriution (M w /M n ) were determined y GPC in THF ginst PS stndrds 29

30 Tle S15: Results from the homopolymeriztion of nbve initited y 1/1 n/n nbea/al 2 Et 3 Cl 3 in the presene of 2,6-di-tert-utylpyridine (DtBP) in DCM t -2 C. [nbve] =.77 M, [AOEt] = 1 M, [nbea] = 4 mm, [Al 2 Et 3 Cl 3 ] = 4 mm nd [DtBP] =.4 mm. Series Time (h) time PDI P ,3 24, The frtion of the VE monomer onverted into polymer ws mesured y grvimetry of the produt. Mnth = [nbve] /[nbea] time.16 g/mol The verge numer moleulr weight (Mn(GPC) ) nd moleulr weight distriution (M w /M n ) were determined y GPC in THF ginst PS stndrds Tle S16: Results from the homopolymeriztion of CEVE initited y 1/1 n/n nbea/al 2 Et 3 Cl 3 in the presene of 2,6-di-tert-utylpyridine (DtBP) in DCM t -2 C. [CEVE] =.8 M, [AOEt] = 1 M, [nbea] = 4 mm, [Al 2 Et 3 Cl 3 ] = 4 mm nd [DtBP] =.4 mm. Series Time (h) time PDI P ,5 23, 1.41 The frtion of the VE monomer onverted into polymer ws mesured y grvimetry of the produt. Mnth = [CEVE] /[nbea] time 16.2 g/mol The verge numer moleulr weight (Mn(GPC) ) nd moleulr weight distriution (M w /M n ) were determined y GPC in THF ginst PS stndrds Tle S17: Results from the homopolymeriztion of SiDEGVE initited y 1/1 n/n nbea/al 2 Et 3 Cl 3 in the presene of 2,6-di-tert-utylpyridine (DtBP) in DCM t -2 C. [SiDEGVE] =.32 M, [AOEt] = 1 M, [nbea] = 4 mm, [Al 2 Et 3 Cl 3 ] = 4 mm nd [DtBP] =.4 mm. Series Time (h) time PDI P ,3 21, The frtion of the VE monomer onverted into polymer ws mesured y grvimetry of the produt. Mnth = [SiDEGVE] /[nbea] time g/mol 3

31 The verge numer moleulr weight (Mn(GPC) ) nd moleulr weight distriution (M w /M n ) were determined y GPC in THF ginst PS stndrds Tle S21: Results from the homopolymeriztion of nbve initited y 1/2 n/n nbea/al 2 Et 3 Cl 3 in the presene of 2,6-di-tert-utylpyridine (DtBP) in n-hex t -2 C. [nbve] = M, [AOEt] = 1 M, [nbea] = 4 mm, [Al 2 Et 3 Cl 3 ] = 8 mm nd [DtBP] =.4 mm. Time of polymeriztion t=48h. Series [nbve] Trgeted DP 48h PDI P21.1 P21.2 P21.3 P ,64 15, 19,28 37,6 9, 12,5 16,72 34, The frtion of the VE monomer onverted into polymer ws mesured y grvimetry of the produt. Mnth = [nbve] /[nbea] 48h.16 g/mol The verge numer moleulr weight (Mn(GPC) ) nd moleulr weight distriution (M w /M n ) were determined y GPC in THF ginst PS stndrds Tle S22: Results from the homopolymeriztion of nbve initited y 1/3 n/n nbea/al 2 Et 3 Cl 3 in the presene of 2,6-di-tert-utylpyridine (DtBP) in n-hex t -2 C. [nbve] = M, [AOEt] = 1 M, [nbea] = 4 mm, [Al 2 Et 3 Cl 3 ] = 12 mm nd [DtBP] =.4 mm. Time of polymeriztion t=48h. Series [nbve] Trgeted DP 48h PDI P22.1 P22.2 P22.3 P ,64 19,3 37,6 5, 6,9 14,4 27,9 37, The frtion of the VE monomer onverted into polymer ws mesured y grvimetry of the produt. Mnth = [nbve] /[nbea] 48h.16 g/mol The verge numer moleulr weight (Mn(GPC) ) nd moleulr weight distriution (M w /M n ) were determined y GPC in THF ginst PS stndrds 31

32 Tle S23: Results from the homopolymeriztion of nbve initited y 1/4 n/n nbea/aletcl 2 in the presene of 2,6-di-tert-utylpyridine (DtBP) in n-hex t -2 C. Time of polymeriztion t=48h. [nbve] = 1.5 M, [AOEt] = 1 M, [nbea] = 4 mm, [Al 2 Et 3 Cl 3 ] = 16 mm nd [DtBP] =.4 mm. Series [nbve] Trgeted DP 48h PDI P ,6 24, 1.33 The frtion of the VE monomer onverted into polymer ws mesured y grvimetry of the produt. Mnth = [nbve] /[nbea] 48h.16 g/mol The verge numer moleulr weight (Mn(GPC) ) nd moleulr weight distriution (M w /M n ) were determined y GPC in THF ginst PS stndrds Tle S24: Results from the homopolymeriztion of SiDEGVE initited y 1/4 n/n nbea/aletcl 2 in the presene of 2,6-di-tert-utylpyridine (DtBP) in n-hex t C. [SiDEGVE] = M, [AOEt] = 1 M, [nbea] = 4 mm, [AlEtCl 2 ] = 16 mm nd [DtBP] =.4 mm. Time of polymeriztion t=42h. Series [SiDEGVE] Trgeted DP x nsidegve 42h PDI P24.1 P24.2 P ,5 12,8 3,8 8, 19,7 3, The frtion of the VE monomer onverted into polymer ws mesured y grvimetry of the produt. Mnth = [SiDEGVE] /[nbea] x SiDEGVE 42h g/mol The verge numer moleulr weight (Mn(GPC) ) nd moleulr weight distriution (M w /M n ) were determined y GPC in THF ginst PS stndrds 32

33 Tle S25: Results from the homopolymeriztion of SiDEGVE initited y 1/4 n/n nbea/aletcl 2 in the presene of 2,6-di-tert-utylpyridine (DtBP) in toluene t C. [SiDEGVE] = M, [AOEt] = 1 M, [nbea] = 4 mm, [AlEtCl 2 ] = 16 mm nd [DtBP] =.4 mm. Time of polymeriztion t=42h. Series [SiDEGVE] Trgeted DP x SiDEGVE 42h PDI P25.1 P ,7 38,2 1,4 19, The frtion of the VE monomer onverted into polymer ws mesured y grvimetry of the produt. Mnth = [SiDEGVE] /[nbea] x SiDEGVE 42h g/mol The verge numer moleulr weight (Mn(GPC) ) nd moleulr weight distriution (M w /M n ) were determined y GPC in THF ginst PS stndrds Tle S26: Results from the homopolymeriztion of CEVE initited y 1/4 n/n nbea/aletcl 2 in the presene of 2,6-di-tert-utylpyridine (DtBP) in toluene t C. [CEVE] = M, [AOEt] = 1 M, [nbea] = 4 mm, [AlEtCl 2 ] = 16 mm nd [DtBP] =.4 mm. Time of polymeriztion t=12h. Series [CEVE] Trgeted DP x CEVE 12h PDI P26.1 P , 37,8 4,4 1, The frtion of the VE monomer onverted into polymer ws mesured y grvimetry of the produt. Mnth = [CEVE] /[nbea] x CEVE 48h 16.2 g/mol The verge numer moleulr weight (Mn(GPC) ) nd moleulr weight distriution (M w /M n ) were determined y GPC in THF ginst PS stndrds 33

34 Controlled tioni polymeriztion of nbve, CEVE nd SiDEVE y Al 2 Et 3 Cl 3 in toluene nd in DCM - Moleulr weight ontrolled together with hin-end termintion. (g.mol -1 ) M w / 3.x x1 4 2.x x1 4 1.x1 4 5.x Toluene: [nbve] =.77 M; [nbea] = 4 mm (P12) Toluene: [CEVE] =.8 M; [nbea] = 4 mm (P13) Toluene: [SiEGVE] =.32 M; [nbea] = 4 mm (P14) DCM:[nBVE] =.77 M; [nbea] = 4 mm (P15) DCM:[SiEGVE] =.32 M; [nbea] = 4 mm (P16) DCM:[CEVE] =.8 M; [nbea] = 4 mm (P17) x VE Fig. S11: Numer verge moleulr weight ( ) nd moleulr weight distriution (M w / ) vs onversion ( x VE ) for the polymeriztion t 2 C in toluene (P12-14) (,, ) nd in dihloromethne (P15-P17) (,,Δ) of.77 M of n-utyl vinyl ether (nbve) (P12, P15) (, ),.8 M of 2-hloroethyl vinyl ether (CEVE) (P13, P16) (, ) nd.32 M of 2-(tert-Butyldimethylsilyloxy) diethylene glyol vinyl ether (SiDEGVE) (P14, P17) (,Δ) initited y 4 mm of nbve-eti id ddut (nbea) in the presene of.4 mm of 2,6 di-tert-utylpyridine (DtBP), 1 M of ethyl ette (AOEt) nd 4 mm of Et 3 Al 2 Cl 3. The totl volume of the solutions (V T ) ws 2 ml for trgeted M n of 2, g/mol t x VE =%. For dditionl experimentl dt, see Tle S12-S17 (Supporting Informtion) 34

35 Controlled tioni polymeriztion of nbve, CEVE nd SiDEVE y Al 2 Et 3 Cl 3 in toluene nd in DCM - Moleulr weight ontrolled together with hin-end termintion. 6 Ln{[VE] /[VE] t } [nbve] =.77 M, [nbea] = 4 mm (P12) [CEVE] =.8 M, [nbea] = 4 mm (P13) [SiDEGVE] =.32 M, [nbea] = 4 mm (P14) (P12): k pp =.275 h -1 (P13): k pp =.69 h -1 (P14): k pp =.24 h x VE Time (h) Fig. S12: First-order kineti (Ln{[VE] /[VE] t }) (full line ) nd onversion ( ) (dsh line ----) vs time for the polymeriztion in toluene t -2 C of.77 M of n-utyl vinyl ether (nbve) (P12) ( ),.8 M of 2- hloroethyl vinyl ether (CEVE) (P13) ( ) nd.32 M of 2-(tert-Butyldimethylsilyloxy) diethylene glyol vinyl ether (SiDEGVE) (P14) ( ) initited y 4 mm of nbve-aeti Aid Addut (nbea) in the presene of 2,6 di-tert-utylpyridine (DtBP), 1 M of ethyl ette (AOEt) nd 4 mm of Et 3 Al 2 Cl 3. The totl volume of the solutions (V T ) is 2 ml for trgeted M n of 2, g/mol t x VE =%. For dditionl experimentl dt, see Tle S12-S14 (Supporting Informtion). x VE 35

36 Controlled tioni polymeriztion of nbve, CEVE nd SiDEVE y Al 2 Et 3 Cl 3 in toluene nd in DCM - Moleulr weight ontrolled together with hin-end termintion. The existene of hin termintion retions in toluene, whih hppening more signifintly for PnBVE tions thn for PCEVE or PSIDEGVE tions (Fig 3(iii) in mnusript), ws lso demonstrted y the filure in yielding well-defined PnBVE 2 --P(nBVE.8 -o-ceve.2 ) (Smple P43) nd PnBVE 2 -- P(nBVE.7 --SiDEGVE.3 ) 5 (Smple P44) t -2 C y sequentil monomer ddition rried out t xnbve 89h < 9%, i.e. on living PnBVE tion showing no signl of UV sorne t 89h < 9% (Fig. 1(ii) in mnusript) PnBVE 2 --P(nBVE.8 -o-ceve.2 ) RI Signl 5 (- - - ) M n = 32 K PDI = 1.39 x (CEVE-nBVE) = 7% 12h PnBVE M n = 19 K PDI = 1.14 = 9% 89h PnBVE 2 --P(nBVE.3 -o-sidegve.7 ) 5 RI Signl (- - - ) Mn = 29 K 5 PDI = 1.45 x (SiDEGVE-nBVE) = 6% 4h PnBVE M n = 19.5 K PDI = 1.16 = 87% 89h Elution volume (ml) Fig. S13: GPC RI tres of poly(n-utyl vinyl ether)--poly(hloro ethyl vinyl ether)(pnbve--pceve) (P42), poly(n-utyl vinyl ether)-lok- ethyl vinyl ether) (PnBVE--PSiDEGVE) (P43) otined y sequentil tioni polymeriztion of nbve nd CEVE (P42) or nbve nd SiDEGVE (P43) in toluene (Tol) t -2 C using 4 mm of the 1/1 n/n 1-utoxyethyl ette /Al 2 Et 3 Cl 3 inititing system in the presene of.4 mm of di--utylypyridine (DtBP) nd 1 M of ethyl ette (AOEt). 36

37 Effet of the [Al 2 Et 3 Cl 3 ]/[nbea] rtio on the living polymeriztion of nbve, CEVE nd SiDEGVE. The use of lrge exess of Al 2 Et 3 Cl 3 (i.e., [Al 2 Et 3 Cl 3 ]/[nbea] = 2 nd 3) to redue the time of polymeriztion did not permit us to produe living PnBVE tions with preditle M n (i.e., sed on the [nbve] /[nbea] rtio) usle for the len synthesis of PnBVE--PCEVE nd PnBVE--PSiEGVE lok opolymers. Fig. S11 shows tht polymers otined t [Al 2 Et 3 Cl 3 ]/[nbea] > 1 nd t [AlEtCl 2 ]/[nbea] > 2 hve s <, inditing tht diret initition from the tlyst n proeed independently of the monomer (i.e., nbve, CEVE, SiDEGVE), the nture of the solvent (i.e., toluene, n-hex nd DCM) nd the temperture of polymeriztion (i.e., T = -2,, 2 C). (g.mol -1 ) 6x1 4 5x1 4 4x1 4 3x1 4 2x1 4-2 C, n-hex, nbve, [Al 2 Et 3 Cl 3 ] /[nbea] =1 (P2) -2 C, n-hex, nbve, [Al 2 Et 3 Cl 3 ] /[nbea] =2 (P21) -2 C, n-hex, nbve, [Al 2 Et 3 Cl 3 ] /[nbea] =3 (P22) -2 C, n-hex, nbve, [AlEtCl 2 ] /[nbea] =4 (P23) C, n-hex, SiDEGVE, [AlEtCl 2 ] /[nbea] =4 (P24) C, Tol, SiDEGVE, [AlEtCl 2 ] /[nbea] =4 (P25) C, Tol, CEVE, [AlEtCl 2 ] /[nbea] =4 (P26) (slope=1) (slope=.73) (slope=.88) (slope=.61) 1x1 4 M w / x1 4 2x1 4 3x1 4 4x1 4 5x1 4 6x1 4 (= [VE] /[nbea] MW VE x VE ) (g.mol -1 ) Fig. S14: Numer verge moleulr weight ( ) nd moleulr weight distriution ( / ) vs theoretil numer verge moleulr weight (M n(th ) dependenes plotted t vrious rtios [tlyst] /[nbea] (= 1, 2 or 3) for the polymeriztion of n-utyl vinyl ether (nbve) (,,, ), 2- hloroethyl vinyl ether (CEVE) ( ) nd 2-(tert-Butyldimethylsilyloxy) diethylene glyol vinyl ether (SiDEGVE) (,Δ) initited y 4 mm of nbve-aeti Aid Addut (nbea) with Al 2 Et 3 Cl 3 (,, ) nd AlEtCl 2 (,,,Δ)) tlyst in the presene of.4 mm of 2,6 di-tert-utylpyridine (DtBP) nd 1 M of ethyl ette (AOEt) in n-hexne (n-hex) (,,,, ) nd toluene (Tol) (,Δ) t nd -2 C. The totl volume of the solutions (V T ) ws 2 ml. Experiments: (P2) ([nbve] =.38,.57,.76, 1.15 nd 1.93, [Al 2 Et 3 Cl 3 ] = [nbea] = 4 mm, 48h = % in n-hex t -2 C) ( ); (P21) ([nbve] =.385,.6,.77 nd 1.5 M, [Al 2 Et 3 Cl 3 ] = 2 x [nbea] = 8 mm, 48h = % in n-hex t -2 C) ( ); (P22) ([nbve] =.385,.77, 1.5 nd 2 M, [Al 2 Et 3 Cl 3 ] = 3 x [nbea] = 12 mm, 48h = % in n-hex t - 2 C) ( ); (P23) ([nbve] = 1.5 M, [AlEtCl 2 ] = 4 x [nbea] = 16 mm, 48h = % in n-hex t -2 C) ( ); (P24) ([SiDEGVE] =.13,.32 nd.5 M, [nbea] = 4 mm, [AlEtCl 2 ] /[nbea] = 4, 48h = % in n-hex t C) ( ); (P25) ([SiDEGVE] =.32 nd.64 M, [nbea] = 4 mm, [AlEtCl 2 ] /[nbea] = 4, 48h < % in Tol t C) ( ); (P26) ([CEVE] =.76 nd 1.5 M, [nbea] = 4 mm, [AlEtCl 2 ] /[nbea] = 4, 48h = % in Tol t C) (Δ). ws lulted ssuming tht one 37

38 polymer hin is formed per moleule of inititor. For dditionl experimentl dt, see Tles S2-S26 in the Supporting Informtion. 38

39 Effet of the [Al 2 Et 3 Cl 3 ] (=[nbea] ) on the living polymeriztion of nbve, CEVE nd SiDEGVE. (g.mol -1 ) 1.x1 5 8.x1 4 6.x1 4 4.x1 4 2.x1 4 [nbve] =.38 to 3.12 M, [nbea] = [Al 2 Et 3 Cl 3 ] = 4 mm (P9) [nbve] = 1.95 to 5.8 M, [nbea] = [Al 2 Et 3 Cl 3 ] = 12 mm (P28) [SiDEGVE] =.2 to 1.6 M, [nbea] = [Al 2 Et 3 Cl 3 ] = 4 mm (P1) [SiDEGVE] =.5 to 3.5 M, [nbea] = [Al 2 Et 3 Cl 3 ] = 12 mm (P29) (y=.89x) (y=x) (y=.81x) M w /M n x1 4 4.x1 4 6.x1 4 8.x1 4 1.x1 5 (=[VE] /[Inititor] MW VE x VE ) (g.mol -1 ) Fig. S15: Numer verge moleulr weight ( ) nd moleulr weight distriution ( / ) vs theoretil numer verge moleulr weight (M n(th ) dependenes plotted t vrious rtios [tlyst] /[nbea] (= 1, 2 or 3) for the polymeriztion of n-utyl vinyl ether (nbve) ( ) nd 2-(tert- Butyldimethylsilyloxy) diethylene glyol vinyl ether (SiDEGVE) ( ) initited y nbve-aeti Aid Addut (nbea) with Al 2 Et 3 Cl 3 (,, ) tlyst in the presene of.4 mm of 2,6 di-tert-utylpyridine (DtBP) nd 1 M of ethyl ette (AOEt) in n-hexne (n-hex) (,,,, ) t -2 C. The totl volume of the solutions (V T ) ws 2 ml. Experiments: (P9) ([nbve] =.38,.78, 1.56 nd 3.12, [Al 2 Et 3 Cl 3 ] = [nbea] = 4 mm, 48h = % in n-hex t -2 C) ( ); (P28) ([nbve] = 1.92, 2.88 nd 4.6 M, [Al 2 Et 3 Cl 3 ] = [nbea] = 12 mm, 48h < 97% in n-hex t -2 C) ( ); (P1) ([SiDEGVE] =.2,.4,.6 nd.8 M, [Al 2 Et 3 Cl 3 ] = [nbea] = 4 mm, 42h< 97% in n-hex t -2 C) ( ); (P29) ([SiDEGVE] = 1.5, 2 nd 3.5 M, [Al 2 Et 3 Cl 3 ] = [nbea] = 12 mm, 48h < 97% in n-hex t -2 C) ( ). ws lulted ssuming tht one polymer hin is formed per moleule of inititor. 39

40 Copolymeriztion of nbve with SiDEGVE The polymeriztion of nbve from 1/1 n/n SiDEGEA/Al 2 Et 3 Cl 3 inititing system in the presene of tiny mount of SiDEGVE (4 nd 1%) yield in n-hex t -2 C polymers with PDI > 1.4 wheres in the sene of SiDEGVE, polymer with PDI < 1.1 were otined (series P27). In this respet, SiDEGVE ws polymerized lst in sequentil monomer ddition.. PnBVE (P27.1) P(nBVE 96 -o-sidegve 4 ) (P27.2) P(nBVE 9 -o-sidegve 1 ) 2 (P27.3) RI Signl Elution volume (ml) Fig. S16 GPC RI tres of poly(n-utyl vinyl ether) (PnBVE) nd -poly(2-hloro ethyl vinyl ether) (PCEVE) (P42) otined in the polymeriztion of nbve (series P276) in n-hexne t -2 C in the presene (---) or in the sene ( ) of tiny mount of (SiDEGVE) (~5-1 %) using 4 mm of the 1/1 n/n SiDEGEA /Al 2 Et 3 Cl 3 inititing system in the presene of.4 mm of di-tert-utylypyridine (DtBP) nd 1 M of ethyl ette (AOEt). For dditionl experimentl dt, see Tles S27 in the Supporting Informtion. Tle S27: Results from the opolymeriztion of nbve with tiny mount of SiDEGVE initited y 1/1 n/n nbea/al 2 Et 3 Cl 3 in the presene of 2,6-di-tert-utylpyridine (DtBP) in nhex t -2 C. [nbve] =.76, [AOEt] = 1 M, [SiDEGEA] = 4 mm, [Al 2 Et 3 Cl 3 ] = 4 mm nd [DtBP] =.4 mm. Time of polymeriztion t=48h. Series [nbve] M P27.1 P27.2 P [SiDEGVE] mm 4 8 Trgeted DP h 19, 19, 19, 19,4 23,5 3,4 The frtion of the VE monomer onverted into polymer ws mesured y grvimetry of the produt. Mnth = [nbve] /[nbea] 48h.16 g/mol The verge numer moleulr weight (Mn(GPC) ) nd moleulr weight distriution (M w /M n ) were determined y GPC in THF ginst PS stndrds PDI