Supporting Information
Synthesis of 4μ-PS2PEO2, 4μ-PS2PCL2, 4μ-PI2PEO2 and
4μ-PI2PCL2 Star-shaped Copolymers by the Combination of
Glaser Coupling with Living Anionic Polymerization and
Ring-opening Polymerization
GUOWEI WANG, XIAOSHAN FAN, JUNLIAN HUANG*
The Key Laboratory of Molecular Engineering of Polymer, State Education Ministry of China, Department of
Macromolecular Science, Fudan University, Shanghai 200433, China
Corresponding author: Junlian Huang; Email: jlhuang@fudan.edu.cn
Preparation of -(n-butyl)--hydroxyl, ’-ethoxyethyl-Poly(styrene) (PS(1)) and -(n-butyl)--hydroxyl,
’-ethoxyethyl-Poly(isoprene) (PI(1)).
Firstly, ethoxyethyl glycidyl ether (EEGE) was synthesized from glycidol and ethyl vinyl ether according to
Fitton et al.1 and distilled under reduced pressure (b.p. 152-154°C), and the purity exceeded 99.7 GC%.2
n-Butyllithium (n-BuLi) was prepared from butyl chloride and lithium metal according to the literature,3 and
analyzed by the double-titration method4 with the concentration of 1.45 mol/L.
S1
The anionic polymerization of styrene or isoprene were carried out according to the literature under the N2
atmosphere,4 where the gas-tight rubber tube was used to seal the reactor and syringe was used to introduce the
reagents. Using the preparation of PS(1) as an example: St (30.00 mL), cyclohexane (210.00 mL) and THF (4.00
mL) were charged into a 500 mL dried ampoule under N2 atmosphere, then the n-Bu-Li+ solution (3.77 mL,
5.467 mmol) was injected by a syringe under magnetic stirring. The reaction was kept at room temperature for
8.0 h, then the mixture of EEGE (3.00 mL, 20.55 mmol) and THF (4.00 mL) was added promptly and the system
was stirred for another 8.0 h before the termination by CH3OH. After the solvents was evaporated, the product
was purified twice by dissolution/precipitation with THF/CH3OH and the obtained white powder of
functionalized polystyrene (PS(1)) was dried under vacuum at 45°C for 24.0 h with a constant weight of 27.1636
g and a 99.61% yield. 1H NMR (CDCl3) δ ppm of PS(1): 0.80(CH3CH2-), 1.13(CH3CH2O-), 1.22(-CH(CH3)-),
1.26-2.01(m, 3H, aliphatic main chain -CH2CH- of PS), 3.09-3.43(m, CH3CH2O-, -CH(OH)CH2O-),
3.52(-CH(OH)-), 4.65-4.76 (-OCH(CH3)O-), 6.30-7.30(m, 5H, aromatic –C6H5 of PS chain). SEC:
Mn(SEC)=4,900 g/mol, PDI=1.03. FT-IR (cm-1): 1600, 1582, 1492, 1452(aromatic -C-C-).
The molecular weight of PS(1) (Mn(NMR,PS(1))=5,000 g/mol ) was calculated according to 1H NMR spectrum
(Figure 2) and Formula S1:
M n(NMR, PS(1)) 
Ag 5
Ah ,i ,l 6
104  57  147
( S1)
Where Ag and Ah,i,j were the integral area of the aromatic protons (-C6H5) at 6.30-7.30 ppm (f) on PS min chain
and the characteristic methylenene group protons (-CH2-) at 3.60 ppm (a) of the capping agent, respectively. The
values of 104 and 57 were the molecular weight of St unit and the mass of the α end initiator residue butyl
group(-C4H9). The value of 147 was the sum between the mass of capping molecule EEGE (C7H14O3) and that of
a proton(-H).
S2
Similarly, the functionalized polyisoprene (PI(1)) was also prepared using the above polymerization
procedure. 1H NMR (CDCl3) δ ppm of PI(2): 0.80 (CH3CH2-), 1.13(CH3CH2O-), 1.22 (m, -CH(CH3)-),
1.26-2.25 (m, -C(CH3)-and aliphatic main chain -CH2CH- of PI), 1.86 (m, -C(CH3)=CH-, -C(CH3)=CH2),
3.09-3.43 (m, CH3CH2O-, -CH(OH)CH2O-), 3.52 (-CH(OH)-), 4.65-4.76 (-OCH(CH3)O-), 4.63-4.69
(-(CH3)C=CH2 of 3, 4-addition), 4.95 (-CH=CH2 of 1,2-addition), 5.08 (-CH=C(CH3)- of 1,4-addition), 5.70
(-CH=CH2 of 1,2-addition). SEC: Mn(SEC)=4,600 g/mol, PDI=1.05. FT-IR (cm-1): 3070(=C-H), 1642(-C=C-),
886(=CH2).
According to the 1H NMR spectrum (Figure 2), the percentage content of 1,2-Addition (C1,2-Addition),
3,4-Addition (C3,4-Addition) and 1,4-Addition (C1,4-Addition) on isoprene units could be determined by using Formula
S2 and the molecular weight of PI(1) (Mn(NMR,PI(1))=4,800 g/mol ) was calculated by using the Formula S3:
C1,2-Addition :C3,4-Addition: C1,4-Addition  A k :
Mn(NMR, PI(1)) 
Ak
Ar , s ,v 6
Ah
:(A l ,o -2A k )
2
 C1,2 Addition  68  57  147
( S 2)
( S 3)
Where Ao, Ak, Ah and Ar,s,v were the integral area of the methine protons (-CH=C(CH3)-) at 5.08ppm (o),
methine protons (-CH=CH2) at 5.70ppm (k), methylene protons (-(CH3)C=CH2) at 4.63-4.69ppm and methylene
protons (-CH2-) at 3.60ppm, respectively. The value of 68 was the molecular weight of isoprene unit.
Preparation of -(n-butyl)--propargyl, ’-ethoxyethyl-Poly(styrene) (PS(2)) and Preparation of
-(n-butyl)--propargyl, ’-ethoxyethyl-Poly(isoprene) (PI(2)).
Into a 500 mL dried ampoule, 26.0201g dried PS(1) (Mn(NMR)(1)=5,000 g/mol, 5.204 mmol) and 270 mL THF
were added. Then, the system was charged with N2 and titrated by DPMK solution till to the solution changed
into reddish-brown. After the ampoule was placed into ice bath, propargyl bromide (3.91 mL, 6.145g, 52.04
S3
mmol) was added dropwise during 2.0 h and the reaction was continued for 24.0 h at room temperature. The
PS(2) was achieved by separation of the formed salts and then purified twice by dissolution/precipitation with
THF/CH3OH, and dried under vacuum at 45°C for 12.0 h till to a constant weight (25.6298 g, 98.50% yield). 1H
NMR (CDCl3) δ (ppm): 0.80(CH3CH2-), 1.13(CH3CH2O-), 1.22(m, -CH(CH3)-), 3.09-3.59(m, CH3CH2O-,
-CH(O-)CH2O-), 3.84-4.18 (-OCH2C≡CH), 4.65-4.76 (-OCH(CH3)O-). FT-IR (cm-1): 3300(-C≡CH).
The efficiency of transformation of hydroxyl groups into alkyne groups (E.F.PS(2)=99.52%) was calculated
according to 1H NMR spectrum (Figure 2) and Formula S4:
E.F.PS(2) =
An 2
x100%
Ah,i,l 6
(S4)
Where An were the integral area of methylene group protons (-OCH2C≡CH) at 3.84-4.18 ppm(n).
Similarly, the functionalized polyisoprene (PI(2)) was also prepared using the above modification
procedure. 1H NMR (CDCl3) δ ppm of PI(2): 0.80 (CH3CH2-), 1.13(CH3CH2O-), 1.22 (m, -CH(CH3)-),
3.09-3.59 (m, CH3CH2O-, -CH(O-)CH2O-), 3.84-4.18 (-OCH2C≡CH), 4.65-4.76 (-OCH(CH3)O-). FT-IR (cm-1):
3300(-C≡CH), 3070(=C-H), 1642(-C=C-), 886(=CH2).
The efficiency of transformation of hydroxyl groups into alkyne groups (E.F.PI(2)=99.70%) was calculated
according to 1H NMR spectrum (Figure 2) and Formula S5:
E.F.PI(2) =
Ax 2
x100%
A r,s,v 6
(S5)
Where Ax was the integral area of methylene group protons (-OCH2C≡CH) at 3.84-4.18 ppm(n).
S4
Figure S1. The FT-IR spectra of 4μ-PS2PEO2 and 4μ-PS2PCL2.
Figure S2. The FT-IR spectra of 4μ-PI2PEO2 and 4μ-PI2PCL2.
S5
REFERENCES AND NOTES
1. Fitton, A. O.; Hill, J.; Jane, D. E.; Millar, R. Synthesis 1987, 1140-1142.
2. Li, Z. Y.; Li, P. P.; Huang, J. J Polym Sci, Part A: Polym Chem 2006, 44, 4361-4371.
3. Wei, J.; Huang, J. Macromolecules, 2005, 38, 1107-1113.
4. Gilman, H.; Haubein, A. H. J Am Chem Soc 1944, 66, 1515-1516.
S6