Fluorinated styrene-based monomers for cyclopolymerizations

Article abstract of DOI:10.1016/j.jfluchem.2011.07.021

The synthesis of versatile fluorine compounds and monomers for conducting polymer research and cyclopolymerizations is presented. Semiprotected 2,3,5,6-tetrafluoroterephthaldehyde 1 could be elaborated through Wittig olefination chemistry, deprotection and reduction to the previously unknown 4-vinyl-2,3,5,6-tetrafluorobenzylalcohol 8 in good yields. Compound 8 can be reacted to form the malonate ester, and then alkylation on the malonate moiety in mild conditions affords difunctional monomer 3. Through sequential esterifications on the malonate moiety, and subsequent alkylation, compound 4, a difunctional monomer for cyclopolymerization bearing one styrene and one perfluoroaryl styrene moiety, has been obtained. Preliminary experiments show that it is possible to cyclopolymerize 4 under free radical conditions.

Full text of DOI:10.1016/j.jfluchem.2011.07.021

Journal of Fluorine Chemistry 132 (2011) 956–960
Contents lists available at ScienceDirect
Journal of Fluorine Chemistry
journal homepage: www.elsevier.com/locate/fluor
Fluorinated styrene-based monomers for cyclopolymerizations
Arvind K. Sharma a,1, Dario Pasini a,b,1,
*
a Department of Chemistry, University of Pavia, Via Taramelli, 10 – 27100 Pavia, Italy
b INSTM Research Unit, University of Pavia, Via Taramelli, 10 – 27100 Pavia, Italy
A R T I C L E I N F O
A B S T R A C T
Article history:
The synthesis of versatile fluorine compounds and monomers for conducting polymer research and
cyclopolymerizations is presented. Semiprotected 2,3,5,6-tetrafluoroterephthaldehyde 1 could be
elaborated through Wittig olefination chemistry, deprotection and reduction to the previously unknown
4-vinyl-2,3,5,6-tetrafluorobenzylalcohol 8 in good yields. Compound 8 can be reacted to form the
malonate ester, and then alkylation on the malonate moiety in mild conditions affords difunctional
monomer 3. Through sequential esterifications on the malonate moiety, and subsequent alkylation,
compound 4, a difunctional monomer for cyclopolymerization bearing one styrene and one perfluoroaryl
styrene moiety, has been obtained. Preliminary experiments show that it is possible to cyclopolymerize
4 under free radical conditions.
Received 27 April 2011
Received in revised form 19 July 2011
Accepted 19 July 2011
Available online 26 July 2011
Keywords:
Tetrafluorobenzene derivatives
Fluorinated monomers
Fluorinated polymers
Cyclopolymerization
ß 2011 Elsevier B.V. All rights reserved.
1. Introduction
with styrene; using controlled ATRP polymerizations, block
copolymers have also been synthesized [8]. Reports using 4-
The control of monomer sequences in synthetic functional
polymers is an underdeveloped area of research [1]. This level of
control is instead ordinarily achieved in natural biopolymers. In
cyclopolymerization processes, two things can be performed at the
same time: make polymers efficiently and generate cyclic
structures in the polymer backbone, addressing polymer rigidity
and stereocontrol [2]. In addition, alternation of monomeric
fragments possessing different chemical structures and reactivities
towards the propagating free radicals can be achieved during
cyclopolymerizations [2d,3]. Polystyrene-like cyclopolymers have
to be designed carefully, since both cyclization into large ring
repeating units and propagation need to be obtained. Following
early work of Wulff [4] and Kakuchi [5], we (monomer 1 in Fig. 1)
and others, have demonstrated how, in diluted conditions,
difunctional styrenic monomers can efficiently generate homo-
cyclopolymers (polymer 2 in Fig. 1) [6,7].
substituted-2,3,4,5-tetrafluorostyrene derivatives are instead less
frequent [9].
Given the different reactivity of aryl perfluorinated styrenes
(such as 2,3,4,5,6-pentafluorostyrene) vs. styrene in free radical
polymerizations [10], we were eager to explore the synthesis and
characterization of difunctional monomers such as 3 and 4 (Fig. 1),
in order to evaluate their reactivity in cyclopolymerizations, and
the potential of monomer 4 for the formation of macromolecules
with alternating nonfluorinated/perfluorinated aryl moieties
within the rigid polymer backbone.
In this paper, we report the synthesis and the characterization
of novel key aryl fluorinated styrene derivatives, their further
manipulation for the synthesis of monomers 3 and 4, and
preliminary data for their cyclopolymerization under free radical
conditions.
Fluorinated polymers are materials that have attracted signifi-
cant attention due to a series of favourable properties, such as high
thermal stability, hydrophobicity, and good chemical resistance.
To the best of our knowledge, only a few aryl fluorinated styrene
monomers have been reported, and used in free radical poly-
merizations. 2,3,4,5,6-Pentafluorostyrene has previously been
polymerized through radical polymerization, or copolymerized
2. Results and discussion
Following our previous work [6b], the insertion of styrene
derivatives into the malonate skeleton was approached via the
esterification of malonyl chloride with suitably modified 4-vinyl
perfluorinated benzyl alcohols. We have shown that dialkylated
malonate moieties, in fact, can ‘‘orient’’ the two styrene fragments
in 1, and therefore facilitate cyclization during propagation. 4-
Vinyl-2,3,5,6-tetrafluorobenzylalcohol 8 was previously reported,
to the best of our knowledge, only in a patent, where its synthesis
was not described [11]. Our approach for its synthesis was to
develop Wittig olefination chemistry on the monoprotected
derivative 5 (Scheme 1) [12]; we had successfully reproduced in
* Corresponding author at: Department of Chemistry, University of Pavia, Via
Taramelli, 10 – 27100 Pavia, Italy. Tel.: +39 0382 987835; fax: +39 0382 987323.
E-mail address: dario.pasini@unipv.it (D. Pasini).
1
Group website: www.unipv.it/labt.
0022-1139/$ – see front matter ß 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.jfluchem.2011.07.021

A.K. Sharma, D. Pasini / Journal of Fluorine Chemistry 132 (2011) 956–960
957
Fig. 1. Difunctional monomers undergoing efficient cyclopolymerization under free
radical conditions.
Fig. 2. 1H NMR spectra of monomer 4 (top) and polymer 13 (bottom) after
purification.
deprotection reaction was conducted following a reported protocol
for compound 5 [12], and had to be monitored by 1H NMR;
compound 7 was used in the following step without further
purification. Reduction with NaBH4 in classical conditions afforded
the key benzylic alcohol 8 (Scheme 1).
Esterification of 8 using malonyl chloride, following conditions
developed for the synthesis of monomer 1, gave malonate ester 9 in
moderate yields, after purification by column chromatography. Its
subsequent alkylation gave monomer 3 in 72% yields (Scheme 2).
All novel compounds were characterized by NMR (1H and 13C), and
elemental analysis.
A statistical approach for the synthesis of monomer 4 (that is,
the reaction of malonyl chloride with one equivalent each of 4-
vinylbenzyl chloride 10 and the fluorinated analogue 8) did not
yield the target compound in reasonable yield. The synthesis of 4,
Scheme 1. Synthesis of 4-vinyl-2,3,5,6-tetrafluorobenzylalcohol 8.
our laboratories the synthesis of 5 in multigram quantities, in the
process of making symmetrically 1,4-functionalized-2,3,5,6-tetra-
fluorobenzene derivatives [13]. Compound 6 was obtained in
reasonable yields after purification by column chromatography,
and deprotected (TFA, H2O, HCl) to give compound 7. The
Table 1
Cyclopolymerization of monomers 1, 3 and 4 under free radical conditions.
c
Entrya
Monomer
[M]/[%AIBN]b
Mn
PDIc
DPd
Yield%e
Polymer
1f
2g
3
1
3
4
0.2/5
0.2/5
0.2/5
6980
2.0
–
18
–
60
–
2
–
–
14920
2.8
32
30
13
a
Polymerizations were run at 70 8C in toluene for 48 h (entry 1) or 90 8C in toluene for 60 h (entry 2 and 3).
b
c
[M] refers to the monomer concentration in toluene, and [%AIBN] is the molar percentage of initiator with respect to monomer.
As determined by GPC relative to polystyrene standards. PDI =polydispersity index.
Degree of polymerization; calculated on the basis of Mn.
d
e
Yield determined on the basis of the molecular weight of monomer after purification by filtration of eventual crosslinked material and precipitation in the nonsolvent
(MeOH).
f
Data taken from Ref. [6b].
g
Oligomeric material was obtained, which could not be purified further by precipitation in a nonsolvent.

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A.K. Sharma, D. Pasini / Journal of Fluorine Chemistry 132 (2011) 956–960
Scheme 3. Synthesis of fluorinated monomer 4 and its cyclopolymerization.
therefore, was approached through a sequential, stepwise func-
tionalization protocol. The malonate monoester 11 could be
obtained by reaction of malonyl dichloride with compound 10 (one
equivalent each), and subsequent hydrolysis of the remaining acid
chloride functionality Scheme 3). The structure of 11 could be
confirmed by 1H NMR spectroscopy. Regeneration of the acid
chloride, and esterification with compound 8, using the previously
applied conditions, afforded compound 12, which could be purified
by chromatography. Finally, alkylation under mild basic conditions
as before afforded the functionalized monomer 4.
characterized. Comparing entry 1 and entry 3 in Table 1, the aryl
fluorinated difunctional monomer 4 gives a slightly higher degree
of polymerization, but also lower isolated yields and higher
poyldispersities, with respect to 1. The 1H NMR of the purified,
precipitated polymer (Fig. 2), when compared with that of the
starting monomer 4, shows that efficient cyclization and propaga-
tion had occurred, as there are no pendant vinyl resonances
present in the 1H NMR spectra, typical of efficient cyclopolymer-
ization processes.
Preliminary experiments for the cyclopolymerization of 3 and 4
were conducted using AIBN as the free radical initiator, as reported
in Table 1. Using the optimized conditions for monomer 1,
3. Conclusions
We have presented a synthetic approach to styrene and
perfluoroarylstyrene difunctional monomers for cyclopolymeriza-
tion. The unknown precursor 4-vinyl-2,3,5,6-tetrafluorobenzylal-
cohol 8 can be synthesized in good yields and multigram
quantities. We have identified good synthetic strategies for the
synthesis of symmetrical asymmetrical difunctional styrenic
monomers 3 and 4. These versatile fluorinated monomers have
the potential to be used to replace their styrene counterparts in
other molecules and polymers. We have studied and characterized
in a preliminar way their ability to undergo cyclopolymerization.
We aim, in further studies, to optimize the cyclopolymerization
conditions for monomers 3 and 4, and to study, in combination
with other difunctional monomers with styrene moieties with
differing reactivities, the propensity of alternation of these
molecular systems, under free radical or controlled free radical
cyclopolymerization conditions.
monomer
3 did not afford polymeric materials, but rather
oligomeric species, difficult to further purify and characterize;
with monomer 4, instead, cyclopolymer 13 could be obtained and
4. Experimental
4.1. General
All commercially available reagents and solvents were used as
received. THF and diethyl ether (Na, benzophenone) and CH2Cl2
(CaH2) were dried and distilled before use. Compounds 5 [12], and
10 [14], were obtained following previously published procedures.
Flash chromatography was carried out using silica gel (Merck 60).
1H and 13C-NMR spectra were recorded from solutions in CDCl3 on
Bruker 200 or AMX300 with the solvent residual proton signal or
tetramethylsilane (TMS) as a standard. Size-exclusion chromatog-
raphy was carried out on a Waters system equipped with a DRI
Scheme 2. Synthesis of fluorinated monomer 3.

A.K. Sharma, D. Pasini / Journal of Fluorine Chemistry 132 (2011) 956–960
959
detector. Low polydispersity polystyrene standards were used for
the calibration curve, and the mobile phase was tetrahydrofuran
(1 mL/min, 40 8C). A bank of two columns (Styragel 4E and 5E) in
series was used. Elemental analyses were done on a Carlo Erba
1106 elemental analyzer.
(0.10 g, 72%). 1H NMR (300 MHz, CDCl3):
CH2CH3), 1.94 (q, 2H, J = 7.6; CH2CH3), 5.22 (s, 4H; ArCH2O–), 5.78
(d, 2H, J = 11.9; CH55CH2), 6.15 (d, 2H, J = 18; CH55CH2), 6.71 (dd,
2H, J = 18, 11.9; CH55CH2). 13C-NMR (75 MHz, CDCl3):
54.3, 58.4, 112.0 (t, J = 17.3), 117.7 (t, J = 13.35), 122.9, 124.3 (t,
J = 7.5), 144.2 (dm, J = 240), 145.1 (dm, J = 248), 170.6. Anal. calcd.
for C25H20F8O4: C 59.7%, H 3.7%; found: C 59.9%; H 3.6%.
d
= 0.81 (t, 3H, J = 7.6;
d = 8.0, 24.6,
Compound 6: to a suspension of methyl triphenylphosphonium
bromide (9.4 g, 0.026 mol) in dry ether (80 mL) at À20 8C under
nitrogen, n-BuLi (11.6 mL, 2.5 M) was added dropwise. The
resulting pink coloured solution was stirred at 0 8C for 2 h. After
this time, this solution was transferred to a solution of compound 5
(6 g, 0.024 mol) in dry ether (40 mL), prepared in a separate flask
under N2 atmosphere. The resulting red coloured reaction mixture
was stirred overnight at room temperature, followed by the
addition of H2O. The organic layer was separated and the aqueous
layer was extracted with ether. The combined organic layers were
dried (Na2SO4), the solvent removed under reduced pressure and
the residue purified by column chromatography over silica gel
(hexanes/AcOEt 99.8/0.02) affording pure compound 6 (2.5 g, 42%).
Compound 11: malonyl dichloride (0.7 g, 5 mmol) was dis-
solved in CH2Cl2 (30 mL) and solution cooled to 0 8C in ice-bath
followed by addition of Et3N (0.75 mL, 0.54 mmol) and DMAP
(5 mg). A solution of compound 10 (0.75 g, 5 mmol) in CH2Cl2
(15 mL) was added dropwise over 2 h. The reaction mixture was
stirred overnight at room temperature. The reaction was quenched
with solution of Na2CO3, aqueous layer separated, acidified with
1N HCl and extracted with CH2Cl2. Combined CH2Cl2 extracts were
dried (Na2SO4) and concentrated under reduced pressure to afford
compound 11 which was used as such without further purification
(0.27 g, 25%). 1H NMR (200 MHz, CDCl3):
d = 3.49 (s, 2H; –
1H NMR (300 MHz, CDCl3):
d
= 4.05–4.20 (m, 4H; –OCH2CH2O–),
OOCCH2COO–), 5.20 (s, 2H; ArCH2O–), 5–28 (d, 1H, J = 11;
CH55CH2), 5.77 (d, 1H, J = 17.6; CH55CH2), 6.73 (dd, 1H, J = 17.6,
11; CH55CH2), 7.28–7.45 (m, 4H; –C6H4–), 8.12 (bs, 1H; –COOH).
Compound 12: compound 10 (0.27 g, 1.2 mmol) was dissolved in
CH2Cl2 followed by the addition of oxalyl chloride (1 mL, excess).
Resulting solution was stirred overnight at room temperature and
concentrated to dryness under reduced pressure. Meanwhile, a
separate solution of alcohol 8 (0.2 g, 0.88 mmol), Et3N (0.17 mL,
1.2 mmol) and DMAP (5 mg) in CH2Cl2 was cooled to 0 8C and a
solution of compound 10 was added to it dropwise. After stirring
reaction overnight 1N HCl was added and aqueous layer extracted
with CH2Cl2. Combined CH2Cl2 extracts were dried (Na2SO4) and
concentrated underreduced pressureto afford crudematerial which
was purified by column chromatography (SiO2: hexanes/AcOEt 98/
2) to afford compound 12 (0.14 g, 40%). 1H NMR (200 MHz, CDCl3):
5.75 (1H, d, J = 11.7; CH55CH2), 6.15 (1H, d, J = 11.7; CH55CH2), 6.24
(1H, s; acetal CH–), 6.69 (1H, m; CH55CH2). Anal. calcd. for
C11H8F4O2: C 53.2%, H 3.2%; found: C 52.9%; H 3.0%.
Compound 7: compound 6 (1.5 g, 6.05 mmol) was slowly added
with stirring to trifluoroacetic acid (5 mL, excess), followed by
addition of H2O (5 mL) and HCl 37% (2 mL). After 3 h stirring at
60 8C, the mixture was cooled to room temperature. The solution
was extracted with CH2Cl2, the organic phase was washed with
H2O (10 mL) and the solvent was removed under reduced pressure
to afford desired compound 7 (1 g, 81%). 1H NMR (200 MHz,
CDCl3):
d = 5.77 (d, 1H, J = 11.7; CH = CH2), 6.14 (d, 1H, J = 11.7;
CH = CH2), 6.71 (m, 1H; CH = CH2), 10.03 (s, 1H; –CHO).
Compound 8: a solution of compound 7 (1 g, 4.9 mmol) in MeOH
(20 mL)wascooledto0 8Cinanice bathand NaBH4 (0.3 g, 7.9 mmol)
added portionwise. The reaction was then stirred at room
temperature for 4 h. MeOH was removed from reaction mixture
under reduced pressure, the residue was taken in H2O, extracted
with CH2Cl2, and the combined organic layers were dried (Na2SO4)
and concentrated to dryness. The residue was purified by column
chromatography (SiO2: hexanes/AcOEt 8/2) to afford pure com-
pound 8 (0.7 g, 69%). 1H NMR (300 MHz, CDCl3):
d = 2.41 (bs, 1H; –
CH2OH), 4.83 (s, 2 H; –CH2OH), 5.74 (d, 1H, J = 11.8; CH55CH2), 6.15
(d, 1H, J = 18.2; CH55CH2), 6.70 (dd, 1H, J = 18.2, 11.8; CH55CH2). 13C-
d
= 3.48 (s, 2H; –OOCCH2COO–), 5.17 (s, 2H; ArCH2O–), 5.26 (s, 2H;
ArCH2O–), 5.77 (d, 2H; CH55CH2), 6.15 (d, 2H; CH55CH2), 6.61–6.71
(m, 2H; CH55CH2), 7.28–7.42 (m, 4H; –C6H4–).
Compound 4: a solution of compound 12 (0.065 g, 0.16 mmol),
Cs2CO3 (0.06 g, 0.2 mmol) and ethyl iodide (0.06 g, 0.32 mmol) in
DMF (2 mL) was stirred overnight at room temperature. H2O
(10 mL) was added to reaction mixture and extraction was done
with diethyl ether. Combined extracts were dried (Na2SO4), and
purified by column chromatography (SiO2: hexanes/AcOEt 98/2) to
give pure compound 4 (0.065 g, 90%). 1H NMR (200 MHz, CDCl3):
NMR (75 MHz, CDCl3):
d = 52.7, 105.8 (t, J = 22.5), 116.8 (t, J = 18),
122.2, 123.8 (t, J = 7.5), 144.3 (dm, J = 249), 144.8 (dm, J = 248). Anal.
calcd. for C9H6F4O: C 52.4%, H 2.9%; found: C 52.7%; H 3.0%.
Compound 9: a solution of alcohol 4 (0.5 g, 2.4 mmol), DMAP
(5 mg), dry Et3N (0.67 mL, 4.8 mmol) in dry CH2Cl2 (20 mL) was
cooled to 0 8C with an ice bath. Malonyl dichloride (0.2 mL,
1.2 mmol) was added dropwise over a 10 min period. The solution
was left stirring at 0 8C for 1 h, overnight at room temperature and
at reflux for 4 h. After cooling, H2O (40 mL) was added, the organic
phase separated, dried (Na2SO4) and the residue purified by
column chromatography (SiO2: hexanes/AcOEt 95/5) to yield 9 as a
d = 0.83 (t, 3H; CH2CH3), 1.96 (q, 2H; CH2CH3), 5.11 (s, 2H; ArCH2O–
), 5.22 (s, 2H; ArCH2O–), 5.76 (d, 2H; CH55CH2), 6.14 (d, 2H;
CH55CH2), 6.60–6.72 (m, 2H; CH55CH2), 7.21–7.39 (m, 4H; –C6H4–).
Anal. calcd. for C25H24F4O4: C 69.8%, H 5.1%; found: C 69.5%; H 5.4%.
Polymer 13: monomer 4 (80 mg) and the initiator (AIBN, 5 mol%
vs. monomer) were dissolved in toluene (at
a monomer
concentration of 0.5 M). The solution was deoxygenated by
bubbling N2 for 30 min and then heated under magnetic stirring
at 90 8C in a temperature-controlled oil bath. The solvent was then
removed under reduced pressure, the remaining solid was
dissolved in a minimum amount of CH2Cl2, filtered from insoluble
material and the solution was added dropwise to MeOH (20 times
its cosolvent volume). The purified, precipitated polymer sample
was filtered and dried (24 mg, 30%). 1H NMR (200 MHz, CDCl3):
colourless oil (0.30 g, 52%). 1H NMR (300 MHz, CDCl3):
d = 3.47 (s,
2H; –OOCCH2COO–), 5.29 (s, 4H; ArCH2O–), 5.78 (d, 2H, J = 11.9;
CH55CH2), 6.18 (d, 2H, J = 18; CH55CH2), 6.71 (dd, 2H, J = 18, 11.9;
CH55CH2). 13C-NMR (75 MHz, CDCl3)
d = 40.7, 54.4, 111.7 (t,
J = 17.3), 117.9 (t, J = 12.8), 122.1, 124.4 (t, J = 7.5), 144.3 (dm,
J = 248), 145.2 (dm, J = 255), 165.2.
d = 0.89 (bs; CH2CH3), 1.97 (bs; CH2CH3), 5.01 (bs; ArCH2O–), 5.90–
7.10 (bs; –C6H4–). Anal. calcd. for (C25H24F4O4)n: C 69.8%, H 5.1%;
Compound 3: a solution of compound 9 (0.13 g, 0.3 mmol),
Cs2CO3 (150 mg, 0.46 mmol) and ethyl iodide (0.1 g, 0.62 mmol) in
DMF (2 mL) was stirred overnight at room temperature. Then H2O
(10 mL) was added to reaction mixture and extraction was done
with Et2O. Combined extracts were dried (Na2SO4), concentrated
under reduced pressure and product purified by column chroma-
tography (SiO2: hexanes/AcOEt 98/2) to afford pure compound 3
found: C 70.1%; H 4.8%.
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