156  US  9,104,101 B2  155  Polymer Synthesis Example 1  Synthesis of Polymeric Compound 1  EXAMPLES  Monomer Synthesis Example  Synthesis of Compound (01)  A  '  Na  [Chemical Formula 78]  Mo~o CH,c,,m,o  B  o~)<;  s  I  ~o  Go  (01)  [Chemical Formula 77]  (a0-0-1)  Details regarding this polymeric compound of the present  invention are the same as described above within the descrip› tion of the component (Al) of the resist composition of the  present invention.  In the formula, R represents a hydrogen atom, an alkyl group  of 1 to 5 carbon atoms or a halogenated alkyl group of 1 to 5  carbon atoms,  R 0 - 1  represents a single bond or a divalent  linking group, each ofR  2 , R $^{3 }$and R$^{4 }$independently represents  a linear, branched or cyclic alkyl group which may have a  non-aromatic substituent, or alternatively R 3  and R 4  may be  bonded to each other to form a ring together with the sulfur  atom in the formula, andX represents a non-aromatic divalent  linking group or a single bond.  A more detailed description of the present invention is  presented below based on a series of examples, although the  present invention is in no way limited by these examples.  In the examples, a compound represented by a chemical  formula (01) is designated as "compound (01 )", and the same  labeling system applies for compounds represented by other  formulas.  In the NMR analyses, tetramethylsilane (TMS) was used as  an internal standardforthe $^{1}$H-NMRand $^{13}$C-NMRmeasure› ments, and hexafluorobenzene was used as an internal stan› dard for the $^{19}$F-NMR measurements (with the hexafluo› robenzene peak designated as -160 ppm).  Of the monomers used in the polymer synthesis examples  described below, the compound (01) was synthesized via a  monomer synthesis example described below. Compounds  (02) to (05) were synthesized in a similar manner.  A round-bottom flask was charged with a compound A (2. 8  g), a compound B (3.8 g), dichloromethane (26 g) and pure  water (26 g), and the resulting mixture was stirred for 30  minutes at room temperature. Subsequently, the dichlo› romethane layer was washed with a 1  % aqueous solution of  hydrochloric acid, and was then washed repeatedly with pure  water (26 g) until neutral. The organic layer was then concen› trated under reduced pressure, yielding 4.7 g of a compound  (01) as a white powder.  The obtained compound was analyzed by NMR, and the  structure was identified on the basis of the results shown  below.  $^{1}$H-NMR (400 MHz, DMSO-d6):  Ii  (ppm)=6.1 (s, lH,  CH$_{2}$=C), 5.74 (s, lH, CH$_{2}$=C), 4.58 to 4.67 (t, 2H, CH$_{2}$),  1.89 (s, 3H, CH$_{3}$ )  $^{19}$F-NMR (376 MHz, DMSO-d6):  Ii  (ppm)=-111.3  In a separable flask fitted with a thermometer, a reflux  condenser and a nitrogen inlet tube, 19 .86 g ( 62. 79 mmol) of  a compound (21), 31.77 g (121.09 mmol) of a compound (11)  and 8.37 g (15.95 mmol) of the compound (01) were dis› solved in 79.53 g of a mixed solvent of methyl ethyl ketone  (MEK) and cyclohexanone (CH). Subsequently, 29.97 mmol  of dimethyl azobisisobutyrate (V-601) was added to, and  dissolved in, the solution as a polymerization initiator. The  resulting solution was added dropwise, over a period of four  hours and under a nitrogen atmosphere, to 42.28 g of MEK  that was heated to 80°  C. Following completion of the drop› wise addition, the reaction solution was stirred for one hour  under heat, and was then cooled to room temperature. The  thus obtained reaction polymerization solution was added  dropwise to a large volume of n-heptane to precipitate the  polymer, and the precipitated white powder was separated by  filtration, washed with methanol, and subsequently dried,  yielding 35.47 g of a polymeric compound 1 as the target  compound.  For this polymeric compound, the polystyrene-equivalent  weight-average molecular weight (Mw) determined by GPC  measurement was 4,300, and the molecular weight dispersity  (Mw/Mn) was 1.87.  Further, the compositional ratio of the copolymer (the pro› portion (molar ratio) of each of the structural units within the  structural formula) determined by carbon-13 nuclear mag› netic resonance spectroscopy (600 MHz,  $^{13}$C-NMR) was 1/rn/  n=45.9/44.0/10.1. 