<p> Supplementary Information</p><p>Precise Synthesis of Poly(1-Adamantyl Methacrylate) by Atom</p><p>Transfer Radical Polymerization</p><p>Keita Fuchise,1 Masako Sone,1 Yutaka Miura,1 Ryosuke Sakai,1 Atsushi Narumi,2</p><p>Shin-Ichiro Sato,1 Toshifumi Satoh,1 and Toyoji Kakuchi1*</p><p>1 Division of Biotechnology and Macromolecular Chemistry, Graduate School of Engineering,</p><p>Hokkaido University, Sapporo 060-8628, Japan</p><p>2 Department of Polymer Science and Engineering, Graduate School of Science and Engineering,</p><p>Yamagata University, Jonan 4-3-16, Yonezawa, 992-8510, Japan</p><p>Tel & Fax: +81-11-706-6602. E-mail: [email protected]</p><p>† Hokkaido University.</p><p>1 Table S1. Atom transfer radical polymerization (ATRP) of 1-adamantyl methacrylate (AdMA) using</p><p> 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</p><p>M (kg mol−1) Temp. Time Conv. n d mm/mr/rr run Mw/Mn e b theo. obsd. (°C) (h) (%) c d</p><p>7 20 15.0 93.9 20.9 21.2 1.85 3/28/69</p><p>8 −20 0.5 10.9 2.5 2.4 1.26 n.d.f</p><p>9 −20 1.0 24.3 5.5 7.6 1.33 n.d. f</p><p>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.</p><p>Figure S1. Expanded 13C NMR spectra of (a) the poly(1-adamantyl methacrylate) (PAdMA) prepared at</p><p>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</p><p>CuBr/CuBr2/Me6TREN catalytic system (mm/mr/rr = 1/21/78, Table S1, run 11).</p><p>2 Scheme S1. Preparation of the poly(1-adamantyl methacrylate) (PAdMA) having bromine</p><p> end-functionality and the block copolymerization of methyl methacrylate (MMA) and the</p><p>PAdMA</p><p>−1 Figure S2. The SEC traces of (a) the PAdMA (Mn = 9.6 kg mol , Mw/Mn = 1.08) synthesized by the</p><p>ATRP of AdMA in toluene at 60 °C for 6 h using the MBiB/CuBr/CuBr2/HMTETA initiating system</p><p>−1 (conditions; [AdMA]0 = 1.14 mol L ; [AdMA]0/[MBiB]0/[CuBr]0/[CuBr2]0/[HMTETA]0 =</p><p>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 =</p><p>−1 1.14 mol L ; [MMA]0/[PAdMA]0/[CuBr]0/[CuBr2]0/[HMTETA]0 = 100/1/1/0.2/1.2).</p><p>3 Figure S3. Differential scanning calorimetry (DSC) trace for the PAdMA (Table 1, run 3, Mn = 8.3 kg</p><p>1 mol− , Mw/Mn = 1.13).</p><p>4</p>