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Supplementary Information

Precise Synthesis of Poly(1-Adamantyl Methacrylate) by Atom

Transfer Radical Polymerization

Keita Fuchise,1 Masako Sone,1 Yutaka Miura,1 Ryosuke Sakai,1 Atsushi Narumi,2

Shin-Ichiro Sato,1 Toshifumi Satoh,1 and Toyoji Kakuchi1*

1 Division of Biotechnology and Macromolecular Chemistry, Graduate School of Engineering,

Hokkaido University, Sapporo 060-8628, Japan

2 Department of Polymer Science and Engineering, Graduate School of Science and Engineering,

Yamagata University, Jonan 4-3-16, Yonezawa, 992-8510, Japan

Tel & Fax: +81-11-706-6602. E-mail: [email protected]

† Hokkaido University.

1 Table S1. Atom transfer radical polymerization (ATRP) of 1-adamantyl methacrylate (AdMA) using

the methyl -bromoisobutyrate (MBiB)/CuBr/CuBr2/tris[2-(dimethylamino)ethyl]amine (Me6TREN) initiating system in 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP)a

M (kg mol−1) Temp. Time Conv. n d mm/mr/rr run Mw/Mn e b theo. obsd. (°C) (h) (%) c d

7 20 15.0 93.9 20.9 21.2 1.85 3/28/69

8 −20 0.5 10.9 2.5 2.4 1.26 n.d.f

9 −20 1.0 24.3 5.5 7.6 1.33 n.d. f

10 −20 1.5 47.8 10.7 9.4 1.33 n.d. f 11 −20 40.5 83.9 18.7 14.1 1.14 1/21/78 a −1 b [AdMA]0/[MBiB]0/[CuBr]0/[CuBr2]0/[Me6TREN]0 = 100/1/1/0.2/1.2; [AdMA]0 = 1.85 mol L . Determined by GC from the concentration of the residual monomer with HFIP as the internal standard. c d Calculated from [AdMA]0/[MBiB]0 × conv. × (M.W. of AdMA = 220.31) + (M.W. of MBiB = 181.03) e 13 Determined by SEC using PMMA standards in CHCl3. Determined by C NMR measurements using the inverse-gated decoupling. f Not determined.

Figure S1. Expanded 13C NMR spectra of (a) the poly(1-adamantyl methacrylate) (PAdMA) prepared at

60 °C in toluene using the CuBr/1,1,4,7,10,10-hexamethyltriethylenetetramine (HMTETA) the catalytic system (mm/mr/rr = 4/27/69, Table 1, run 3) and (b) the PAdMA prepared at −20 °C in HFIP using the

CuBr/CuBr2/Me6TREN catalytic system (mm/mr/rr = 1/21/78, Table S1, run 11).

2 Scheme S1. Preparation of the poly(1-adamantyl methacrylate) (PAdMA) having bromine

end-functionality and the block copolymerization of methyl methacrylate (MMA) and the

−1 Figure S2. The SEC traces of (a) the PAdMA (Mn = 9.6 kg mol , Mw/Mn = 1.08) synthesized by the

ATRP of AdMA in toluene at 60 °C for 6 h using the MBiB/CuBr/CuBr2/HMTETA initiating system

−1 (conditions; [AdMA]0 = 1.14 mol L ; [AdMA]0/[MBiB]0/[CuBr]0/[CuBr2]0/[HMTETA]0 =

100/1/1/0.2/1.2) and (b) the resultant mixture of the block copolymerization of MMA and the PAdMA using the CuBr/CuBr2/HMTETA catalytic system in toluene at 60 °C for 9 h (conditions; [MMA]0 =

−1 1.14 mol L ; [MMA]0/[PAdMA]0/[CuBr]0/[CuBr2]0/[HMTETA]0 = 100/1/1/0.2/1.2).

3 Figure S3. Differential scanning calorimetry (DSC) trace for the PAdMA (Table 1, run 3, Mn = 8.3 kg

1 mol− , Mw/Mn = 1.13).