Synthesis and characterization of fluorine-containing PAA-b-PTPFCBPMA amphiphilic block copolymer

Article abstract of DOI:10.1002/pola.24347

A series of perfluorocyclobutyl (PFCB) aryl ether-based amphiphilic diblock copolymers containing hydrophilic poly(acrylic acid) (PAA) and fluorophilic poly(p-(2-(p-tolyloxy)perfluorocyclobutoxy)phenyl methacrylate) segments were synthesized via successive atom transfer radical polymerization (ATRP). 2-MBP-initiated and CuBr/N,N,N′,N′,N″- pentamethyldiethylenetriamine-catalyzed ATRP homopolymerization of the PFCB-containing methacrylate monomer, p-(2-(p-tolyloxy)perfluorocyclobutoxy) phenyl methacrylate, can be performed in a controlled mode as confirmed by the fact that the number-average molecular weights (M_n) increased linearly with the conversions of the monomer while the polydispersity indices kept below 1.38. The block copolymers with narrow molecular weight distributions (M_w/M_n & 1.36) were synthesized by ATRP using Br-end-functionalized poly(tert-butyl acrylate) (PtBA) as macroinitiator followed by the acidolysis of hydrophobic PtBA block into hydrophilic PAA segment. The critical micelle concentrations of the amphiphilic diblock copolymers in different surroundings were determined by fluorescence spectroscopy using N-phenyl-1-naphthylamine as probe. The morphology and size of the micelles were investigated by transmission electron microscopy and dynamic laser light scattering, respectively.

Full text of DOI:10.1002/pola.24347

Synthesis and Characterization of Fluorine-Containing
PAA-b-PTPFCBPMA Amphiphilic Block Copolymer
YONGJUN LI,1,2 SEN ZHANG,1 HAO LIU,1 QINGNUAN LI,2 WENXIN LI,2 XIAOYU HUANG1
1Key Laboratory of Organofluorine Chemistry and Laboratory of Polymer Materials, Shanghai Institute of Organic Chemistry,
Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, People’s Republic of China
2Laboratory of Nano-Biology and Medicine, Shanghai Institute of Applied Physics, Chinese Academy of Sciences,
2019 Jialuo Road, Shanghai 201800, People’s Republic of China
Received 9 July 2010; accepted 26 August 2010
DOI: 10.1002/pola.24347
Published online 5 October 2010 in Wiley Online Library (wileyonlinelibrary.com).
ABSTRACT: A series of perfluorocyclobutyl (PFCB) aryl ether-
based amphiphilic diblock copolymers containing hydrophilic
poly(acrylic acid) (PAA) and fluorophilic poly(p-(2-(p-tolyloxy)-
perfluorocyclobutoxy)phenyl methacrylate) segments were
synthesized via successive atom transfer radical polymeriza-
tion (ATRP). 2-MBP-initiated and CuBr/N,N,N0,N0,N00-pentame-
thyldiethylenetriamine-catalyzed ATRP homopolymerization
of the PFCB-containing methacrylate monomer, p-(2-(p-toly-
loxy)perfluorocyclobutoxy)phenyl methacrylate, can be per-
formed in a controlled mode as confirmed by the fact that the
number-average molecular weights (Mn) increased linearly
with the conversions of the monomer while the polydisper-
sity indices kept below 1.38. The block copolymers with nar-
synthesized by ATRP using Br-end-functionalized poly(tert-
butyl acrylate) (PtBA) as macroinitiator followed by the acid-
olysis of hydrophobic PtBA block into hydrophilic PAA seg-
ment. The critical micelle concentrations of the amphiphilic
diblock copolymers in different surroundings were deter-
mined by fluorescence spectroscopy using N-phenyl-1-naph-
thylamine as probe. The morphology and size of the micelles
were investigated by transmission electron microscopy and
C
V
dynamic laser light scattering, respectively. 2010 Wiley Peri-
odicals, Inc. J Polym Sci Part A: Polym Chem 48: 5419–5429,
2010
KEYWORDS: atom transfer radical polymerization; block copoly-
row molecular weight distributions (Mw/Mn
ꢀ
1.36) were
mers; perfluorocyclobutyl; self-assembly; synthesis
INTRODUCTION Since the discovery of perfluorocyclobutyl
(PFCB) aryl ether polymers by Babb et al. of Dow Chemical
Co. in early 1990s,1–4 this partially fluorinated polymer
has attracted much interests in many fields such as optical
applications,5–8 aerospace coating materials,9 and battery
electrolyte applications.10 In comparison with traditional
fluoropolymers, PFCB aryl ether-based polymers exhibited
not only high thermal and thermal oxidative stability, chemi-
cal resistance, and superior electrical insulating ability but
also improved processability, which solved to some extent
the manufacturing problem of fluoropolymers because of
high crystallinity.11 To synthesize this kind of fluoropolymer,
a relatively unusual reaction, thermal [2p þ 2p] step-growth
cyclopolymerization of trifluorovinyl ether (TFVE), was
adopted to provide new thermoplastics and thermosets pos-
sessing PFCB aromatic ether linkage.12 As an effective cou-
pling method, this initiator-free reaction without the emis-
sion of small molecule byproducts has been used in the
synthesis of many PFCB-based polymers with potential appli-
cations in photonics, polymer light emitting diodes, proton
exchange membranes for fuel cells, atomic oxygen resistant
coatings, and hybrid composites.13
However, because of its unique polymerization mechanism,
PFCB aryl ether-based polymers were often prepared from
homopolymerization or random copolymerization of the fluo-
rine-containing monomers bearing two or three TFVE func-
tionalities. Until now, none has reported the incorporation of
PFCB groups into commonly used monomers which can be
polymerized by conventional chain growth polymerization
approaches. Therefore, the variety and application of PFCB
aryl ether-based polymers has been obviously limited.
Recently, our group has developed a novel type of (meth)acry-
late monomers with PFCB-containing ester group,14,15 which
can be polymerized via traditional AIBN-initiated free radical
polymerization to afford poly(meth)acrylate possessing PFCB
pendent groups (Scheme 1). When controlled/‘‘living’’ radical
polymerization was applied, it enabled us to obtain tailor-
made PFCB aryl ether-based homo- or copolymers with well-
defined architecture and function, which has certainly wid-
ened the application of PFCB-based fluoropolymers.
The self-assembly of fluoropolymers has been well investi-
gated for decades. In comparison with the hydrocarbon poly-
mers, fluorinated polymers are more rigid and less miscible
Correspondence to: X. Huang (E-mail: xyhuang@mail.sioc.ac.cn) or Q. Li (E-mail: liqingnuan@sinap.ac.cn)
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Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 48, 5419–5429 (2010) 2010 Wiley Periodicals, Inc.
FLUORINE-CONTAINING PAA-b-PTPFCBPMA, LI ET AL.
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JOURNAL OF POLYMER SCIENCE: PART A: POLYMER CHEMISTRY DOI 10.1002/POLA
tert-butyl acrylate, and butyl acrylate,43 and been taken as
one of the most powerful methods to synthesize various
well-defined copolymers.
In this work, we present the synthesis of a new well-defined
PFCB aryl ether-based amphiphilic block copolymer, poly
(acrylic acid)-b-poly(p-(2-(p-tolyloxy)perfluorocyclobutoxy)-
phenyl methacrylate) (PAA-b-PTPFCBPMA), via sequential
ATRP of tert-butyl acrylate and p-(2-(p-tolyloxy)perfluorocy-
clobutoxy)phenyl methacrylate (TPFCBPMA) followed by the
selective acidolysis of hydrophobic poly(tert-butyl acrylate)
(PtBA) block (Scheme 2). Moreover, the aqueous self-assem-
bly behavior of the amphiphilic diblock copolymer has been
studied by measuring the critical micelle concentrations
(cmc) and the size of the micelles, and visualizing the micel-
lar morphologies.
SCHEME 1 Comparison of structures between the main-chain
PFCB-based polymer (A) with the PFCB-pending polymethacry-
late (B).
EXPERIMENTAL
Materials
tert-Butyl acrylate (tBA, Aldrich, 98%) was washed with 5%
aqueous NaOH solution to remove the inhibitor, then washed
with water, dried over CaCl2, and distilled twice over CaH2
under reduced pressure before use. Copper (I) bromide
(CuBr) (Aldrich, 99%) was purified by stirring overnight
over CH3COOH at room temperature followed by washing
the solid with ethanol, acetone, and diethyl ether before dry-
because of their fluorophobic effect. Therefore, the replace-
ment of hydrocarbon block with fluorinated block in amphi-
philic copolymers can imbue favorable properties to nanoma-
terials such as high thermal stability, chemical resistance,
excellent mechanical properties at extreme temperatures, and
low refractive index (RI). Percec et al.16–29 reported fluori-
nated liquid crystal molecules with perfluorinated alkane
chains, which can produce a microsegregation at the molecu-
lar levels, and this process can be alone responsible for the
formation of lamellar thermotropic and lyotropic mesophases.
Ni et al. prepared amphiphilic hyperbranched star-block co-
polymers containing polycations and fluoropolymer seg-
ment,30 which can directly self-organize into supramolecular
multicompartment micelles with different diameters. Although
these interesting results were concerned with the polymers
with flexible fluorinated alkane side chains, seldom have been
reported on the self-assembly behaviors of amphiphilic
copolymers bearing rigid fluorine-containing side groups,
which may self-assemble into much different nanostructures.
ꢁ
ing at 40 C in vacuo for 1 day. 1,2-Dibromotetrafluoroethane
was prepared by condensing equimolar amounts of Br2 and
tetrafluoroethylene at ꢂ195 ꢁC followed by warming up to
Block copolymers are macromolecules composed of linear
arrangements of chemically different polymeric chains
(blocks) which give rise to a rich variety of well-defined self-
assembled structures both in bulk and selective solvents.31,32
Generally, synthesis of block copolymers is conducted by
sequential addition of different monomers via living poly-
merization. Progress in polymer synthesis techniques makes
it possible to produce block copolymers with a specified
monomer composition. Synthesis of block copolymer via
ionic living polymerization has to be run under stringent
conditions. Recently, various living radical polymerizations
including stable free radical polymerization,33–35 atom trans-
fer radical polymerization (ATRP),36–39 reversible addition
fragmentation chain transfer (RAFT)40 polymerization, and
single electron transfer-living radical polymerization (SET-
LRP)41,42 have been frequently used to prepare block copoly-
mers under mild conditions. In particular, ATRP has been
successfully used for the polymerization of a variety of com-
mon (meth)acrylate monomers, such as methyl methacrylate,
SCHEME 2 Synthesis of PAA-b-PTPFCBPMA Amphiphilic Diblock
Copolymer.
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ARTICLE
22 ꢁC according the previous literature.44 Granular zinc was
activated by washing in 0.1 M HCl followed by drying at
140 ꢁC in vacuo for 10 h. N-Phenyl-1-naphthylamine (PNA)
(Alfa Aesar, 97%) was purified by recrystallization in ethanol
for three times. 4-Methoxyphenol (Aldrich, 99%), 4-bromo-
phenol (Aldrich, 99%), N,N,N0,N0,N00-pentamethyldiethylene-
triamine (PMDETA, Aldrich, 99%) methyl 2-bromopropionate
(2-MBP, Acros, 99%), and methacryloyl chloride (Alfa Aesar,
97%) were used as received.
Demethylation of 4-(2-(p-tolyloxy)perfluorocyclobutoxy)ani-
sole was carried out by treating with BBr3. To a solution of
4-(2-(p-tolyloxy)perfluorocyclobutoxy)anisole (13.67 g, 0.035
mol) in CH2Cl2 (240 mL), BBr3 (1 M in CH2Cl2, 70 mL, 0.07
mol) was added dropwise at 0 ꢁC for 1 h. The mixture was
warmed to room temperature and stirred overnight. Metha-
nol (10 mL) was added to terminate the reaction followed
by washing the mixture with brine and dried over Na2SO4.
After concentration, the desired phenol, 4-(2-(p-tolyloxy)per-
fluorocyclobutoxy)phenol (light brown oil), was obtained by
flash chromatography (hexane: ethyl acetate ¼ 10:1) with a
quantitative yield. 1H NMR: d(ppm): 2.32 (s, 3H), 5.30 (s,
1H), 6.79 (dd, 2H), 7.08 (m, 6H). 19F NMR: d(ppm): ꢂ128.6
to ꢂ131.8 (m, cyclobutyl-F6). EI-MS: m/z 378.
The above-prepared phenol (3.0 g, 0.008 mol) and triethyl-
amine (0.93 mL, 0.0096 mol) were dissolved in 25 mL of 2-
butanone, and the mixture was stirred at 0–5 ꢁC. Methacry-
loyl chloride (1.4 mL, 0.0096 mol) in 10 mL of 2-butanone
was added dropwise within 30 min, and the mixture was
stirred for another 1 h. Finally, the mixture was stirred at
room temperature for 1 h. The precipitated triethylammo-
nium chloride was filtered, and the filtrate was washed twice
with water. The solution was dried over Na2SO4 followed by
the concentration to remove the solvent, 2-butanone. The
monomer, TPFCBPMA 1 (colorless oil), was obtained by flash
column chromatograph (hexane: ethyl acetate ¼ 100:1) with
a yield of 87.0%. FT-IR (KBr): m (cmꢂ1): 2930, 1740 (C¼¼O),
1638, 1503, 1319, 1187, 1123, 962 (PFCB), 817. 1H NMR:
d(ppm): 2.06 (s, 3H), 2.32 (s, 3H), 5.78 (s, 1H), 6.35 (s, 1H),
7.12 (m, 8H). 19F NMR: d(ppm): ꢂ128.4 to ꢂ132.4 (m,
cyclobutyl-F6). 13C NMR: d(ppm): 18.3, 20.6, 117.8, 117.9,
119.2, 119.5, 121.2, 122.7, 122.8, 126.9, 127.4, 129.9, 130.1,
130.2, 134.8, 135.3, 136.0, 147.8, 148.0, 148.7, 149.7, 149.9,
150.2, 165.6. EI-MS: m/z 446. HRMS: C21H16O4F6, calcd.
446.0953, found 446.0964.
Measurements
FT-IR spectra were recorded on a Nicolet AVATAR-360 FT-IR
spectrophotometer with a resolution of 4 cmꢂ1. EI-MS was
measured by an Agilent 5937N system. High resolution mass
spectrometer (HRMS) was recorded on a Waters Micromass
GCT instrument. All NMR analyses were performed on a
Bruker Avance 500 spectrometer (500 MHz). Tetramethylsi-
lane (TMS) (1H NMR) and CDCl3 13C NMR) were used as
(
internal standards and CF3CO2H was used as an external
standard for 19F NMR. Conversion of TPFCBPMA was deter-
1
mined by H NMR. Relative molecular weights and molecular
weight distributions were measured by a Waters gel permea-
tion chromatography (GPC) system equipped with a Waters
1515 Isocratic HPLC pump, a Waters 2414 RI detector and a
set of Waters Styragel columns (HR3 (500–30,000), HR4
(5000–600,000), and HR5 (50,000–4000,000), 7.8 ꢃ 300
mm). GPC measurements were carried out at 35 ꢁC using
tetrahydrofuran (THF) as eluent with a flow rate of 1.0 mL/
min. The system was calibrated with linear polystyrene
standards. Steady-state fluorescence spectra of PNA were
measured on a Hitachi F-4500 spectrofluorometer with the
bandwidth of 5 nm for excitation and emission; the emission
intensity at 418 nm was recorded to determine the cmc with
an excitation wavelength (kex) of 340 nm. TEM images were
obtained by a JEOL JEM-1230 instrument operated at 80 kV.
Hydrodynamic diameter (Dh) was measured by dynamic
laser light scattering (DLS) with a Malvern Nano-ZS90
Zetasizer.
ATRP of TPFCBPMA Initiated by 2-MBP
ATRP of the fluorine-containing methacrylate TPFCBPMA
was initiated by 2-MBP using CuBr/PMDETA as catalytic sys-
tem in 2-butanone to obtain the corresponding homopoly-
mer with narrow molecular weight distribution. In a typical
procedure, a 10-mL Schlenk flask (flame-dried under vacuum
before use) with a magnetic stir bar was charged with CuBr
(10.0 mg, 0.07 mmol), TPFCBPMA (0.936 g, 2.1 mmol),
PMDETA (14.6 lL, 0.07 mmol) and 2-butanone (1 mL). The
flask was sealed with a rubber septum and degassed by
three freezing-pumping-thawing cycles. The flꢁask was then
immersed into an oil bath thermostated at 70 C and 2-MBP
(7.8 lL, 0.07 mmol) was added slowly to start the polymer-
ization. The polymerization was terminated by putting the
flask into liquid N2 after 8 h. After repeated purification by
dissolving in THF and precipitating in methanol for three
times, PTPFCBPMA 2a was obtained after drying in vacuo at
40 ꢁC. GPC: Mn ¼ 12,500, Mw/Mn ¼ 1.36. 1H NMR: d(ppm):
1.37 (CCH3), 1.47, 1.75 (CH2), 2.28 (C6H4CH4), 3.61
(COOCH3), 6.98, 7.06 (phenyl). 19F NMR: d (ppm): ꢂ127.8 to
ꢂ132.7 (m, cyclobutyl-F6).
Synthesis of TPFCBPMA
p-(Trifluorovinyloxy)toluene and p-(trifluorovinyloxy)anisole
were first prepared from 4-methoxyphenol and 4-bromophe-
nol, respectively, via standard fluoroalkylation followed by
Zn-mediated dehalogenation in good yield.1 Next, p-(trifluor-
ovinyloxy)toluene (20 mL, 0.13 mol) and p-(trifluorovinyloxy)-
anisole (25 mL, 0.15 mol) were added to a predried flask,
and the mixture was heated at 170 ꢁC for 12 h under N2.
The cross-dimer 4-(2-(p-tolyloxy)perfluorocyclobutoxy)ani-
sole of a colorless oil was obtained by column chromatogra-
phy (hexane: ethyl acetate ¼ 100:1) with a yield of 51.6%.
1H NMR: d(ppm): 2.32 (s, 3H), 3.78 (d, 3H), 6.86 (dd, 2H),
7.10 (m, 6H). 19F NMR: d(ppm): ꢂ128.6 to ꢂ131.8 (m,
cyclobutyl-F6). 13C NMR: d (ppm): 20.5, 20.6, 55.4, 55.5,
114.5, 114.6, 118.0, 118.4, 119.8, 120.1, 122.9, 130.0, 130.1,
134.7, 135.0, 145.9, 146.2, 150.3, 150.5, 156.9, 157.1, 157.9.
FT-IR (KBr): m (cmꢂ1): 2956, 2860, 1507, 1193, 962 (PFCB).
EI-MS: m/z 392. HRMS: C18H14O3F6, calcd. 392.0847, found
392.0865.
FLUORINE-CONTAINING PAA-b-PTPFCBPMA, LI ET AL.
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JOURNAL OF POLYMER SCIENCE: PART A: POLYMER CHEMISTRY DOI 10.1002/POLA
TABLE 1 ATRP Homopolymerization of TPFCBPMA 1a
b
T
Mn
b
c
Sample [1]:[2-MBP] (ꢁC) (g/mol) Mw/Mn
NTPFCBPMA
2a
2b
a
30:1
50:1
70
50
12,500
6,200
1.36
1.23
28
14
[2-MBP]:[PMDETA]:[CuBr] ¼ 1:1:1.
b
c
Measured by GPC in THF at 35 ꢁC.
The number of TPFCBPMA repeating unit obtained from GPC.
Synthesis of PAA-b-PTPFCBPMA
PAA-b-PTPFCBPMA amphiphilic diblock copolymer was syn-
thesized by ATRP block copolymerization of TPFCBPMA initi-
ated by Br-terminated PtBA macroinitiator followed by the
selective acidolysis of PtBA block. In a typical procedure,
TPFCBPMA (0.936 g, 2.1 mmol), PtBA 3a (Mn ¼ 6100, Mw/
Mn ¼ 1.10, 0.255 g, 0.042 mmol Br end group), CuBr (6.0
mg, 0.042 mmol), PMDETA (17.5 lL, 0.084 mmol), and 2-
butanone (1 mL) were added into a 10-mL Schlenk flask
(flame-dried under vacuum before use) sealed with a rubber
septum and degassed by three freezing-pumping-thawing
cycles. The flꢁask was then immersed into an oil bath thermo-
stated at 60 C to start the polymerization, and the polymer-
ization was terminated by putting the flask into liquid N2 af-
ter 18 h. The reaction mixture was dissolved in 5 mL THF
and then passed through a short alumina column to remove
the residual copper catalyst. PtBA-b-PTPFCBPMA 4a diblock
copolymer was precipitated into methanol followed by dry-
FIGURE 1 FT-IR spectrum of TPFCBPMA 1.
Preparation of Br-End-Functionalized PtBA
Macroinitiator
In a typical procedure, a predried 10-mL Schlenk flask with
a magnetic stir bar was charged with CuBr (19.6 mg, 0.138
mmol), tBA (2 mL, 13.8 mmol), PMDETA (28.5 lL, 0.138
mmol), and anisole (0.5 mL). The flask was sealed with a
rubber septum and degassed by three freezing-pumping-
thawing cycles. The flask was then immersed into an oil
bath thermostated at 60 ꢁC, and 2-MBP (30.5 lL, 0.276
mmol) was added slowly to start the polymerization, which
was terminated by putting the flask into liquid N2 after 3 h.
The reaction mixture was precipitated into 25 vol % metha-
nol/H2O after passing through an alumina column to remove
the residual copper complexes. The crude product were dis-
solved in ethyl ether and then concentrated, followed by dry-
ing in vacuo at room temperature for 1 day to afford PtBA
ing in vacuo at room temperature for 1 day. GPC: Mn
¼
23,500, Mw/Mn ¼ 1.36. FT-IR (KBr): m (cmꢂ1): 2979, 2929,
1727, 1505, 1323, 1197, 1104, 965. 1H NMR: d(ppm): 1.36,
1.44 (C(CH3)3), 1.53, 1.82 (CH2 of polyacrylate), 2.23 (CH of
polyacrylate), 2.26 (C6H4CH3), 3.66 (COOCH3), 6.98, 7.05
(phenyl). 19F NMR: d(ppm): ꢂ128.4 to ꢂ132.9 (m, cyclobu-
tyl-F6).
1
3a. GPC: Mn ¼ 6100, Mw/Mn ¼ 1.10. H NMR: d (ppm): 1.14
(CHCH3), 1.44 (C(CH3)3), 1.53, 1.82 (CH2CH), 2.23 (CH2CH),
3.65 (COOCH3), 4.09 (CHBr).
Acidolysis of PtBA-b-PTPFCBPMA to PAA-b-PTPFCBPMA was
carried out according to the following procedure. PtBA-b-
PTPFCBPMA 4 was dissolved in dichloromethane and stirred
at room temperature for 2 days with five equivalent of
FIGURE 3 1H NMR (A) and 19F NMR (B) spectra of PTPFCBPMA
2 synthesized by ATRP in 2-butanone.
FIGURE 2 1H NMR (A) and 19F NMR (B) spectra of TPFCBPMA 1.
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ARTICLE
FIGURE 4 Kinetic plot (A) and dependence of molecular weight (Mn) and molecular weight distribution (Mw/Mn) on the conversion
of monomer (B) for solution ATRP of TPFCBPMA 1.
CF3CO2H relative to the amount of tBA units. PAA-b-
PTPFCBPMA 5 amphiphilic diblock copolymer was precipi-
tated into cold n-hexane followed by drying in vacuo at room
temperature for 1 day. FT-IR (KBr): m (cmꢂ1): 3420, 2929,
1752, 1505, 1323, 1197, 1104, 965. 1H NMR: d(ppm): 1.36,
1.53, 1.82 (CH2 of polyacrylate), 2.23 (CH of polyacrylate),
2.26 (C6H4CH3), 3.66 (COOCH3), 6.98, 7.05 (phenyl). 19F
NMR: d (ppm): ꢂ128.4 to ꢂ132.9 (m, cyclobutyl-F6).
motetrafluoroethane followed by Zn-mediated dehalogena-
tion in high yield. Next, the PFCB-containing cross-dimer,
4-(2-(p-tolyloxy)perfluorocyclobutoxy)anisole, was prepared
via thermal [2p þ 2p] cross-coupling reaction of the two
TFVEs in good yield. Finally, synthesis of TPFCBPMA mono-
mer was carried out by demethylation of 4-(2-(p-tolyloxy)-
perfluorocyclobutoxy)anisole and then esterification of the
phenol with methacryloyl chloride.
The chemical structure of TPFCBPMA was examined by FT-
IR, 1H NMR and 19F NMR. The peaks at 962 cmꢂ1 in FT-IR
spectrum (Fig. 1) showed the existence of PFCB group.45,46
Characteristic signals of carbonyl and double bond appeared
at 1740 and 1638 cmꢂ1, respectively. Typical resonance sig-
nals of double bond were located at 5.78 and 6.35 ppm in
1H NMR spectrum of TPFCBPMA as shown in Figure 2(A).
The peaks around 7.12 ppm are attributed to eight protons
of benzene ring in PFCB aryl ether. Furthermore, a series of
peaks between ꢂ127.8 and ꢂ132.7 ppm in 19F NMR spec-
trum [Fig. 2(B)] also verified the existence of PFCB linkage.
All these evidences confirmed the successful synthesis of
TPFCBPMA 1.
Determination of cmc
PNA was used as fluorescence probe to measure the cmc of
PAA-b-PTPFCBPMA 5. Acetone solution of PNA (1 mM) was
added to a large amount of water until the concentration of
PNA reached 0.002 mM. Then, different amounts of THF sol-
utions of PAA-b-PTPFCBPMA 5 (1, 0.1, or 0.01 mg/mL) were
added to water containing PNA ([PNA] ¼ 0.002 mM). All flu-
ꢁ
orescence spectra were recorded at 20 C.
TEM Measurement
Micelles solutions were prepared by two different methods,
the direct dissolution method, and the water addition
method. In the first way, THF solution of PAA-b-PTPFCBPMA
5 (1 mg/mL) was added dropwise to water with vigorous
stirring until the final concentration was 0.05 mg/mL. The
solution was stirred for another several hours for the evapo-
ration of THF. In the second way, 0.4 mL of water was added
slowly (0.8 mL/h) to 0.8 mL of THF solution of the diblock
copolymer 5a (0.1 mg/mL and 10 mg/mL), and THF was
removed by dialysis. For TEM measurement, 10 lL of micel-
lar solution was deposited on an electron microscopy copper
grid coated with carbon film and the water evaporated at
room temperature.
RESULTS AND DISCUSSION
Synthesis of TPFCBPMA Monomer
Synthesis of TPFCBPMA methacrylate monomer was follow-
ing our previously reported procedure.14,15 First, two TFVEs,
p-(trifluorovinyloxy)toluene and p-(trifluorovinyloxy)anisole,
were prepared via standard fluoroalkylation with 1,2-dibro-
FIGURE 5 GPC curves of PTPFCBPMA 2 homopolymers synthe-
sized by ATRP.
FLUORINE-CONTAINING PAA-b-PTPFCBPMA, LI ET AL.
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JOURNAL OF POLYMER SCIENCE: PART A: POLYMER CHEMISTRY DOI 10.1002/POLA
TABLE 2 Preparation of PtBA Macroinitiatora
b
b
c
Sample
Time (h)
Mn (g/mol)
Mw/Mn
NtBA
3a
3b
a
3.5
1.5
6,600
3,800
1.10
1.15
50
33
[tBA]:[2-MBP]:[PMDETA]:[CuBr] ¼ 100:2:1:1, polymerization tempera-
ture: 70 ꢁC.
b
Measured by GPC in THF at 35 ꢁC.
c
The number of tBA repeating unit obtained from GPC.
ATRP Homopolymerization of TPFCBPMA
In general, two different strategies have been adopted to
synthesize the block copolymers: sequential addition of the
monomers and coupling of two appropriately end-functional-
ized chains.31 The first method is the most widely used,
especially after the discovery of living radical polymeriza-
tions such as ATRP,42 RAFT,47 and SET-LRP.48–53 Because of
the wide variety of the monomers, various solvents, conser-
vation of end groups, and control over molecular weights,
we attempted successive ATRP of tBA and TPFCBPMA to
synthesize PAA-b-PTPFCBPMA diblock copolymers.
FIGURE 6 1H NMR spectra of PtBA-b-PTPFCBPMA 4 (A) and
PAA-b-PTPFCBPMA 5 (B).
ATRP of TPFCBPMA monomer was carried out using 2-MBP
as an initiator and CuBr/PMDETA as a catalytic system in 2-
butanone similar to previous report,54 and good control over
the molecular weight distribution (Mw/Mn ¼ 1.36) and a
high molecular weight (Mn ¼ 12,500) was obtained when
Figure 4(A). It can be concluded that the apparent polymer-
ization rate is first order with respect to the concentration
of the monomer. Figure 4(B) shows the evolution of molecu-
lar weights and molecular weight distributions with the con-
versions of TPFCBPMA. It is clear that molecular weights
increase linearly with monomer conversion and the molecu-
lar weight distributions remained narrow throughout the poly-
merization (Mw/Mn < 1.40). Nevertheless, Mn,GPC deviated
significantly from Mn,Cal. At lower conversions (<52%), the
experimental Mn is higher than theoretical values, indicating
a lower initiation efficiency; however, at higher conversions,
there are more chains than theoretically expected, likely a
consequence of additional chains arising from thermal poly-
merization.55 In addition, all PTPFCBPMA 2 homopolymers
obtained by ATRP showed unimodal and symmetrical GPC
ꢁ
the polymerization temperature was 70 C as listed in Table
1. The homopolymer was characterized by 1H NMR [Fig.
3(A)], and ATRP mechanism of the polymerization was con-
firmed by a minor peak at 3.61 ppm, which was corre-
sponded to three protons of COOCH3 in ATRP initiator group.
After polymerization, the signals of vinylidene at 5.78 ppm
and 6.35 ppm disappeared and the signals of the backbone
appeared at 1.37 ppm (CCH3) and 1.47, 1.75 ppm (CH2)
instead. In addition, the preservation of PFCB linkage was
also illustrated by the typical multiplets ranging from
ꢂ127.8 ppm to ꢂ132.7 ppm in 19F NMR spectrum of poly-
merized product.
To confirm the controlled nature of 2-MBP-initiated and
CuBr/PMDETA-catalyzed polymerization of TPFCBPMA, we
studied the polymerization kinetics by 1H NMR to draw
the semilogarithmic plot of ln([M]0/[M]) versus time in
TABLE 3 Synthesis of PtBA-b-PTPFCBPMA Diblock Copolymera
d
Mn
d
e
Sample [1]:[Br group] (g/mol) Mw/Mn
NtBA-b-NTPFCBPMA
4ab
4bb
4cc
4dc
a
100:1
50:1
50:1
50:2
23,500
16,900
18,000
9,800
1.36
1.32
1.33
1.18
50-b-38
50-b-24
33-b-32
33-b-14
[Br group]:[PMDETA]:[CuBr] ¼ 1:1:1, polymerization temperature: 70 ꢁC.
Initiated by 3a (Mn ¼ 6,600, Mw/Mn ¼ 1.10).
b
c
Initiated by 3b (Mn ¼ 3,800, Mw/Mn ¼ 1.15).
d
e
Measured by GPC in THF at 35 ꢁC.
FIGURE 7 GPC curves of PtBA 3 and PtBA-b-PTPFCBPMA 4 in
The composition of the block copolymer obtained from GPC.
THF.
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ARTICLE
FIGURE 9 Dependence of fluorescence intensity ratio of PNA
emission band at 418 nm on the concentration of PAA-b-
PTPFCBPMA 5b.
FIGURE 8 FT-IR spectra of PtBA-b-PTPFCBPMA 4 (A) and PAA-
b-PTPFCBPMA 5 (B).
curves (Fig. 5). These observations suggested that the 2-
MBP-initiated and CuBr/PMDETA-catalyzed polymerization
of TPFCBPMA is seen to be well controlled.36,37
1H NMR, FT-IR and GPC. Figure 6(A) shows 1H NMR spec-
trum of the diblock copolymer. The sharp peak at 1.44 ppm
was attributed to nine protons of C(CH3)3 of PtBA block. The
peaks between 6.90 ppm and 7.15 ppm belonged to eight ar-
omatic protons, and the signal at 2.24 ppm was attributed to
three protons of tolyl in PTPFCBPMA block. The typical sin-
glet of COOCH3 in ATRP initiation group has also been
founded to be located at 3.65 ppm, which indicated that
block copolymerization of TPFCBPMA was initiated from Br-
end-functionalized PtBA 3 macroinitiator.
Synthesis of PAA-b-PTPFCBBMA
We chose tBA for the synthesis of first chain segment
because of its facile acidic cleavage of tert-butyl ester func-
tionality to afford a carboxylic acid-based hydrophilic seg-
ment.56,57 ATRP of tBA and the synthesis of block copolymer
containing PtBA segment have been well studied.58,59 Follow-
ing the previously reported procedure, Br-end-functionalized
PtBA 3 macroinitiators with two different molecular weights
have been prepared first. The molecular weights and polydi-
persity indices of PtBA 3 macroinitiators were measured by
GPC, and the numbers of repeating unit, NtBA, were calcu-
lated from the results of GPC measurement. As seen from
Table 2, both macroinitiators possess 33 and 47 repeating
units, respectively.
GPC traces of PtBA
3
macroinitiators and PtBA-b-
PTPFCBPMA 4 diblock copolymers are shown in Figure 7.
The molecular weights of all copolymers are much higher
than those of the macroinitiators, which demonstrated that
Br-end-functionalized PtBA can act as macroinitiator to initi-
ate the polymerization of TPFCBPMA. Moreover, all GPC
curves of the macroinitiators and the diblock copolymers
exhibited unimodal and symmetrical peaks with narrow mo-
lecular weight distributions (Mw/Mn ꢀ 1.36), which indicate
an almost 100% efficiency of PtBA macroinitiator.58,59
The above prepared Br-end-functionalized PtBA macroinitia-
tors were used to initiate ATRP of TPFCBPMA to synthesize
PtBA-b-PTPFCBPMA 4 diblock copolymer using the CuBr/
PMDETA catalytic system at 70 ꢁC in 2-butanone. The block
length was tuned by varying the feeding ratio of the mono-
mer to the macroinitiator as summarized in Table 3. PtBA-b-
PTPFCBPMA 4 diblock copolymer was well characterized by
Selective acidic hydrolysis of tert-butyl ester groups in PtBA
block was achieved by treating the diblock copolymer with
anhydrous CF3CO2H in dichloromethane at room tempera-
ture for 2 days. Thus, PtBA-b-PTPFCBPMA 4 hydrophobic
TABLE 4 Critical Micelle Concentration of PAA-b-PTPFCBPMA Diblock Copolymer
cmcb (g/mL)
pH ¼ 6
a
Sample
NAA-b-NTPFCBPMA
Pure Water
pH ¼ 4
pH ¼ 9
5a
5b
5c
5d
a
47-b-38
47-b-24
33-b-32
33-b-14
4.16 ꢃ 10ꢂ6
5.01 ꢃ 10ꢂ6
4.72 ꢃ 10ꢂ6
5.37 ꢃ 10ꢂ6
–
–
–
3.01ꢃ10ꢂ6
–
4.27 ꢃ 10ꢂ6
–
6.31 ꢃ 10ꢂ6
–
–
–
–
The composition of the block copolymer.
b
Critical micelle concentration determined by fluorescence spectroscopy using PNA as probe.
FLUORINE-CONTAINING PAA-b-PTPFCBPMA, LI ET AL.
5425

JOURNAL OF POLYMER SCIENCE: PART A: POLYMER CHEMISTRY DOI 10.1002/POLA
ysis [Fig. 8(B)], thus indicating the formation of hydrophilic
PAA block.
Self-Assembly of PAA-b-PTPFCBPMA in Aqueous Media
Critical micelle concentrations (cmc) of PAA-b-PTPFCBPMA
5 diblock copolymers in aqueous solution were determined
by fluorescence technique using PNA as probe. PNA can dis-
play higher fluorescence activity in nonpolar surroundings
and its fluorescence can be very easily quenched by polar
solvents, such as water; moreover, it is a more suitable fluo-
rescent probe than pyrene in terms of reproducibility.60–63
Figure 9 shows the relationship of the fluorescence intensity
ratio (I/I0) of PNA as a function of the concentration of PAA-
ꢁ
b-PTPFCBPMA 5b at 20 C. It is apparent that I/I0 increased
sharply when the concentration of the amphiphilic block co-
polymer exceeded a certain value, which meant PNA probe
was incorporated into the hydrophobic region of micelles.
Thus, the intersection of two straight lines with a value of
5.01 ꢃ 10ꢂ6 g/mL was determined to be cmc of PAA-b-
PTPFCBPMA 5b. The cmc values of PAA-b-PTPFCBPMA 5 are
listed in Table 4, which are slightly lower than those of the
common surfactants or polymeric amphiphiles.64–67 The cmc
behavior of the current fluorine-containing amphiphilic
diblock copolymer is actually analogous with that of common
amphiphilic copolymer.68 The cmc values of PAA-b-
PTPFCBPMA 5 decreased with the increasing of the content
of hydrophobic PTPFCBPMA segment. Moreover, because of
the polyelectrolyte nature of PAA segment, the carboxylic
groups of PAA block would be subject to protonation or ioni-
zation while tuning pH value of the solution, which led to
the decreasing or increasing of the cmc of PAA-b-
PTPFCBPMA.68,69 In acidic aqueous solution, the ionization
of the carboxylic groups of PAA block was suppressed
because of its protonation of reducing the electrostatic repul-
sion among PAA segments; thus, the cmc value decreased
notably compared with that in pure water (from 5.01 ꢃ
10ꢂ6 g/mL in pure water to 4.27 ꢃ 10ꢂ6 g/mL when pH ¼
6 and 3.01 ꢃ 10ꢂ6 g/mL when pH ¼ 4). On the other hand,
the cmc increased remarkably (cmc ¼ 6.31 ꢃ 10ꢂ6 g/mL
FIGURE 10 TEM images of micelles formed by PAA-b-
PTPFCBPMA 5a (A), 5b (B), 5c (C) and 5d (D) in pure water pre-
pared by direct dissolution method.
diblock copolymer was converted to PAA-b-PTPFCBPMA 5
amphiphilic block copolymer, which was recovered from
CH2Cl2 solution by repeat precipitation into cold n-hexane
and dried in vacuo. PAA-b-PTPFCBPMA 5 amphiphilic block
copolymer was characterized by 1H NMR and FT-IR spec-
trum. It is clear that the signal at 1.44 ppm originating from
1
tert-butyl ester groups of PtBA block disappeared in H NMR
spectrum after acidolysis [Fig. 6(B)], and the aromatic ester
group of PTPFCBPMA block remained intact after acidolysis.
Furthermore, a strong sharp band at 965 cmꢂ1 in FT-IR
spectrum [Fig. 8(A)] evidenced the retaining of PFCB rings
in the amphiphilic block copolymers after acidolysis, and a
new broad band at 3420 cmꢂ1 attributed to the newly-
formed carboxyl appeared compared with that before acidol-
FIGURE 11 Hydrodynamic diameter distributions of micelles formed by PAA-b-PTPFCBPMA 5.
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ARTICLE
FIGURE 12 TEM images of micelles
formed by PAA-b-PTPFCBPMA 5a with
different initial concentrations, (A) 10
mg/mL and (B) 0.1 mg/mL.
when pH ¼ 9) in basic aqueous surroundings because of the
end-functionalized PtBA macroinitiator, which were con-
verted to PAA-b-PTPFCBPMA amphiphilic block copolymer
via a readily acidic hydrolysis by CF3CO2H and the aromatic
ester group of PTPFCBPMA block remained intact during the
acidolysis. Self-assembly of PAA-b-PTPFCBPMA in aqueous
solution was studied by fluorescence spectroscopy, TEM and
DLS. The cmc and micellar size of the copolymer were found
to be related with the length of hydrophobic PTPFCBPMA
segment. This type of micelles would throw light on the
potential application of PFCB-containing polymers.
ionization of the carboxylic groups.
PAA-b-PTPFCBPMA 5 block copolymers can aggregate in
aqueous solution to form micelles with PAA-corona and
PTPFCBPMA-core, and different sizes of micelles were
formed with different copolymers as visualized by TEM.
When micellar solutions were prepared by directly adding
the solution of the copolymer into water with vigorous stir-
ring, almost spherical micelle-like aggregates70 with diameter
of ca. 100ꢄ200 nm were formed as shown in Figure 10.
The sizes of the micelles were also measured by DLS (Fig.
11), and it was found that the size of the micelles raised as
the length of PTPFCBPMA segment increased. When
NTPFCBPMA increased from 24 of 5b to 38 of 5a, the diameter
of the micelles enlarged from 127.1 nm to 158.9 nm, so as
do 5d and 5c. As the length of hydrophobic PTPFCBPMA
segment increases, a rising of the aggregation number is
favored because of the decrease in the interface area
between the solvent and PTPFCBPMA segment.71–74 As a
result of increasing of the aggregation number, the size of
spherical core had to increase, that is, the size of micelles
increased.
The authors thank the financial support from National Natural
Science Foundation of China (20674094 and 10775169), Minis-
try of Science and Technology of ‘‘National High Technology
Research and Development Program" (2006AA03Z541).
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