Photopolymerization of maleimide perfluoropolyalkylethers without a photoinitiator

Article abstract of DOI:10.1002/pola.29311

Perfluoropolyalkylethers derived from hexafluoropropylene oxide were functionalized with maleimide groups. Irradiated by UV-light, the new maleimide macromonomers demonstrated very fast polymerization kinetics with a curing time as fast as 8 s. The effect on photopolymerization of different features such as the molecular weight of the fluorinated chain and the chain length of the hydrogenated spacer were studied, as well as the influence of the type of photoinitiator and the presence of air. Thermal and surface properties of the UV-cured polymers were examined and were typical to fluoropolymers in view of water–oil repellent coatings.

Full text of DOI:10.1002/pola.29311

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Photopolymerization of Maleimide Perfluoropolyalkylethers without a
Photoinitiator
1
Céline Bonneaud ,1 Julia M. Burgess,2 Roberta Bongiovanni ,3 Christine Joly-Duhamel
Chadron M. Friesen
,
2
1Ingénierie et Architectures Macromoléculaires, Institut Charles Gerhardt, Ecole Nationale Supérieure de Chimie de Montpellier
(UMR5253-CNRS), 8, rue de l’Ecole Normale, 34296, Montpellier Cedex 5, France
2Department of Chemistry, Trinity Western University, 7600 Glover Road, Langley, British Columbia V2Y 1Y1, Canada
3Department of Applied Science and Technology, Politecnico di Torino, c. Duca degli Abruzzi 24, 10129, Torino, Italy
Correspondence to: C. M. Friesen (E-mail: chad.friesen@twu.ca) and C. Joly-Duhamel (E-mail: christine.joly-duhamel@enscm.fr)
Received 14 November 2018; accepted 10 December 2018
DOI: 10.1002/pola.29311
ABSTRACT: Perfluoropolyalkylethers derived from hexafluoropropy-
lene oxide were functionalized with maleimide groups. Irradiated by
UV-light, the new maleimide macromonomers demonstrated very
fast polymerization kinetics with a curing time as fast as 8 s. The effect
on photopolymerization of different features such as the molecular
weight of the fluorinated chain and the chain length of the hydroge-
nated spacer were studied, as well as the influence of the type of
photoinitiator and the presence of air. Thermal and surface proper-
ties of the UV-cured polymers were examined and were typical to
fluoropolymers in view of water–oil repellent coatings. © 2018 Wiley
Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018
KEYWORDS: perfluoropolyalkylethers; photopolymerization; mal-
eimides; omniphobicity
fluorine content attached to maleimides, ranging from single
fluorines, CF3 to C6F13 moieties. Barrales-Rienda et al.14
reported in 1977 the first synthesis of fluorine-containing
maleimides and their thermal polymerization using 2,20-
azobisisobutyronitrile (AIBN).15 Much later, Mokhtar et al.16
synthesized another maleimide, 4-(4-trifluoromethyl)phenoxy
N-phenyl-maleimide which was also polymerized using AIBN.
Maleimides containing pentafluoro and trifluoro groups on aro-
matics were copolymerized with vinyl ethers by Hendlinger
et al.17 whereas Jain et al.18 copolymerized N-(4-fluoro phenyl)
maleimide with methyl methacrylate. Daukiya et al.19 showed
the use of N-(3,4-trifluoro phenyl) maleimide with highly non-
reactive graphene. Fluorinated oligomers with maleimides were
first reported by Beaune et al. with C6F13 chains.20 Boutevin
et al.21 also demonstrated that maleimide-containing C6F13 moi-
eties can also be grafted onto high density polyethylene. Few
examples of fluorinated telechelic bis(maleimides) can be found
having as spacers a perfluoroalkyl chain22 or fluorinated aro-
matics23 or even difluoromaleimides as telechelic end groups.24
Lastly, maleimides have been found to be useful in medical
applications for radiolabeling. For example, N-(p-[18F]fluorophe-
nyl)maleimide was used to label monoclonal antibodies.25 Vari-
ous maleimide-based compounds were exploited as reagents for
protein, peptide and lipids labeling with thiol functions26–28 and
thus used in positron emission tomography imaging.29,30
INTRODUCTION Photopolymerization is a green process: it
occurs rapidly without a solvent and at room temperature.1
Commonly, photopolymerized systems are constituted of
(meth)acrylates or thiol-enes.2–5 Maleimides are alternative
systems which polymerize almost as fast as acrylates but do
not require a photoinitiator. Indeed, maleimides can initiate
the polymerization on their own as displayed in Scheme 1.
The mechanism of initiation was found to be an electron
transfer, which provides a radical anion. It was supported by
Fourier Transform-Electron Paramagnetic Resonance and by
flash laser photolysis.6,7 Thus, maleimides can homopolymer-
ize without a photoinitiator8 as the presence of photoinitiator
can lead to their leaching or their hard removal if used in
excess. Moreover, maleimides can serve as photoinitiators for
different types of unsaturated resins (acrylate, vinyl ether,
and epoxy).9,10
Various types of maleimides were tested under UV-light such as
poly(propylene glycol)-maleimides8 or silicon-maleimides11,12
and demonstrated the high ability of polymerization of the malei-
mides even in presence of long chains.
Maleimides have been found to be very useful in variety of poly-
mer systems from “click” chemistry, self-healing polymers to
thermoset polymers with high temperature stability.13 However,
the body of work only demonstrated a minimal amount of
Additional supporting information may be found in the online version of this article.
© 2018 Wiley Periodicals, Inc.
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Methods
Photopolymerization by Fourier-Transform–Real Time
Infrared Spectroscopy
Real-time Infrared Spectroscopy and photopolymerization
kinetics were performed on a Thermo Scientific Nicolet 6700
FTIR apparatus by using OMNIC software. A mercury lamp
(OmniCure S2000) was used as UV-light source and OmniCure
R2000 Radiometer was used to control the light output. A radi-
ometer from Solatell provided a real light intensity on the sam-
ple of 10 mW cm−2. A polypropylene film (6 μm) was used as
air protector. The sample was irradiated during 300 s at least.
Four repeats were made for each experiment. No photoinitiator
was added except if specified. The conversion rate calculations
were made by following the disappearance of the band at
826 cm−1 corresponding to the maleimide. They were calcu-
lated using the univariate method (τ = (1 − (A/A0)) × 100).
The peak deconvolution method was used to confirm the quan-
titative conversion. When required, an UV production curing
unit Fusion UV F300S equipped with a microwave lamp (linear
power output of 120 W cm−1) was utilized. The sample was
placed on a LC6B Bench top conveyor and passed repeatedly
SCHEME
mechanism.
1 Homopolymerization of maleimides by radical
In this study, we synthesized new maleimides characterized
by perfluoropolyalkylether (PFPAE) chains, based on hexa-
fluoropropyleneoxide (HFPO) unit CF(CF3)CF2O . The syn-
thesized monomers have a general structure maleimide-Rh-Rf
where Rf = CF3CF2CF2O(CF(CF3)CF2O)n CF(CF3) with n = 5.5
and 10 and Rh
=
(CH2)m(CO)OCH2 with m = 3, 5, 10. The
new monomers were photopolymerized to obtain new poly-
meric materials with promising performances due to the
long fluorinated PFPAES chains. Notably, PFPAE polymers
which contain ether units such as (CF2O) , (CF2CF2O) ,
(CF2CF2CF2O) , and (CF(CF3)CF2O) are known to dem-
onstrate excellent chemical and thermal inertness with low
surface energy. They are not crystalline and are stable from
−100 and 400 ꢀC in the liquid state.31 Moreover, they are
attractive for use since they are non-toxic fluoropolymers in
comparison to some perfluoroalkyl chains and therefore can
be employed in biomedical applications.32–34
under the UV lamp at a speed of travel belt of 1 m min−1
.
Gas Chromatography (GC) Mass Spectrometry (MS)
An Agilent Technologies 6890N GC was coupled with an Agi-
lent Technologies 7638B series injector and Agilent Technolo-
gies 5975B inert mass spectrometer (MSD) was employed
with electron impact as the mode of ionization. The GC was
equipped with a Zebron ZB-5 ms column, 30 m × 0.18 mm id,
0.18 μm df. The detector and the injector temperatures were
200 and 280 ꢀC, respectively. The temperature program
started from 50 ꢀC with a 2 min hoꢀld, then the heating rate
The influences of the molecular weight of the fluorinated
chain, the hydrogenated spacer length as well as the presence
of air and photoinitiator on cure time and thermal degrada-
tion were studied.
−1
ꢀ
ꢀ
was 25 C min until reaching 250 C and holding at 250 C
for 2 min. The total pressure 108 kPa, total flow was
25.9 mL min−1, column flow 0.74 mL min−1, purge flow
3 mL min−1, linear velocity 38 2 cm s−1, and a split injection
of 30:1. The sample was previously diluted in methoxyper-
fluorobutane (3M’s Novec™ HFE-7100) in a GC vial.
EXPERIMENTAL
Nuclear Magnetic Resonance (NMR) spectroscopy
Materials
NMR spectra were recorded on a Bruker AVANCE III 400 MHz
spectrometer instruments using TopSpin 3.5 operating at
400.13 (1H), 376.46 (19F), and 100.62 (13C) MHz at room tem-
perature except if specified. CDCl3 and C6D6 capillaries were
used as internal references. The letters s, d, t, q, quint, sext,
and spt stand for singlet, doublet, triplet, quartet, quintuplet,
sextet and septuplet, respectively.
Glacial acetic acid, 11-maleimidoundecanoïc acid, 6-amin
ocaproic acid, 4-aminobutyric acid, maleic anhydride, thionyl
chloride, triethylamine, dicyclohexylcarbodiimide, 4-dimethyl
aminopyridine, 2-hydroxy-2-methylpropiophenone (Darocur
1173), diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO),
phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (BAPO), dich
loromethane, hexadecane, and deuterated solvents (DMSO-d6,
CDCl3 and C6D6) were purchased from Sigma Aldrich and used
as received except if stated below. 1,1,1,3,3-pentafluorobutane
was purchased from Alfa Aesar. The 1250 g/mol oligo
(HFPO) methylene alcohol was prepared from Krytox®
acyl fluoride. The 1250 g/mol Krytox® acyl fluoride and
2000 g/mol Krytox® methylene alcohol were kindly provided
by the Chemours Company. Triethylamine, hexadecane, and
dichloromethane were dried for 48 h over preconditioned 3 Å
molecular sieves (20% w/v). Thionyl chloride was previously
distilled before use.
Matrix Assisted Laser Desorption Ionization Time-of-Flight
Mass Spectrometry (MALDI-TOF-MS)
The homologue distributions of the products were determined
with a Bruker Autoflex™ MALDI-TOF: spectrometer equipped
with a 1 kHz smartbeam-II laser and reflector in positive ioni-
zation. For sample preparation,
a one drop sample of
poly(HFPO) was added to a 1 mL solution of 50:50 1% LiCl in
MeOH and 2% perfluorocinnamic acid dissolved in 50:50
MeOH:Methoxynonafluorobutane (3 M HFE-7100). A 1 μL
2
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solution was then pipetted on to a ground steel plate, dried,
and irradiated for a minimum of 5000 shots.
6-maleimidohexanoïc acid 1b (yield = 35%): 1H NMR (400 MHz,
CDCl3, δ): 1.3–1.37 (m, CH2 , 2H), 1.56–1.70 (m, CH2 , 4H),
3
3
2.35 (t, JH-H = 7.6 Hz, CH2COOH, 2H), 3.52 (t, JH-H = 7.3 Hz,
NCH2 , 2H), 6.70 (s, CH=CH , 2H), 10.97 (s, COOH, 1H)
13C NMR (101 MHz, CDCl3, δ): δ = 24.1 ( CH2CH2COOH ), 26.1
( NCH2CH2CH2 ), 28.2 ( NCH2CH2 ), 33.8 ( CH2COOH ),
37.6 ( NCH2 , 1C), 134.1 ( CH CH ), 170.9 ( (CO)
CH CH (CO) ), 179.7 ( CH2COOH).
Thermogravimetric Analyses (TGA)
The degradation temperatures were determined with
a
.
NETZSCH TG209F1 at a heating rate of 20 or 10 ꢀC min−1
Approximately 10 mg of the sample was placed in an alumina
ꢀ
crucible and heated from room temperature to 600 C under
inert atmosphere or air (40 mL min−1). To analyze the
evolved gases, the instrument is coupled with a FTIR PER-
SEUS Bruker heated at 200 ꢀC and the obtained spectra are
Synthesis of the Acid Chlorides (2b-c)
To a solution of the corresponding maleimido acid in dry
DCM, 1.5 eq of triethylamine was added with 2 eq of thionyl
chloride. The solution was heated at 50 ꢀC for 3 h. The volatile
compounds were removed under reduced pressure. The prod-
ucts were recovered quantitatively (yield >99%) as orange-
brown solids.
given between 4000 and 600 cm−1
.
Differential Scanning Calorimetry (DSC)
The glass transition temperatures were determined with a
NETZSCH DSC200F3 calorimeter. Constant calibration was
performed using indium, n-octadecane, and n-octane stan-
dards. Ten to fifteen milligrams were placed in pierced alumi-
num pans and the thermal properties were recorded between
−150 and 100 ꢀC at 20 ꢀC min−1. Nitrogen was used as the
purge gas.
6-maleimidohexanoyl chloride 2b (yield>99%): 1H NMR
(400 MHz, CDCl3, δ): 1.26 (m, CH2CH2CH2COCl , 2H), 1.52
(quint, CH2CH2COCl, 2H), 1.64 (quint, NCH2CH2 , 2H),
3
3
2.82 (t, JH-H = 7.6 Hz,
CH2COOH, 2H), 3.42 (t, JH-
= 7.33 Hz, NCH2 , 2H), 6.63 (s, CH CH , 2H). 13C NMR
H
(101 MHz, CDCl3, δ): 24.1 ( CH2CH2COOH ), 26.1
( NCH2CH2CH2 ), 28.2 ( NCH2CH2 ), 33.8 ( CH2COOH ),
37.6 ( NCH2 ), 134.1 ( CH CH ), 170.9 ( (CO) CH CH
(CO) ), 179.7 ( CH2COOCl).
Contact Angle Measurements
The hydrophobicity and oleophobicity were determined;
thanks to a contact angle system OCA20 coupled with a CCD-
camera from DataPhysics Instrument using the software
SCA20 4.1. The measurements were made in air at room tem-
perature by the sessile drop technique with deionized water
or previously dried hexadecane. Three repeats were made on
three different samples previously spin-coated (1 min–
2000 rpm) on glass slides; thanks to Spincoat G3-8 from Spe-
cialty Coating Systems and irradiated thanks to a UV bench
conveyor. Their difference in the average value was not more
than 3ꢀ.
11-maleimidoundecanoyl chloride 2c (yield >99%): 1H NMR
(400 MHz, C6D6, δ): 1.47–1.51 (m, N CH2CH2(CH2)6CH2CH2(CO) ,
3
12H), 1.76 (quint, N CH2CH2(CH2)6 , JH-H = 6.6 Hz, 2H), 1.90
(quint, Cl(CO) CH2CH2(CH2)6 , 2H), 3.12 (t, Cl(CO)CH2
= 7.2 Hz, 2H), 3.67 (t, N CH2
3JH-H = 7.2 Hz, 2H), 6.90
,
3JH-H
,
(s, CH CH , 2H). 13C NMR (101 MHz, C6D6, δ): 24.8 ( NCH2CH2 ),
28.1 ( CH2CH2COOH ), 29.2 ( CH2CH2(CH2)6CH2CH2(CO) ,
33.9 ( NCH2 ), 37.5 ( CH2COOH ), 134.0 ( CH CH ),
172.0 ( (CO) CH CH (CO) ), 179.9 ( CH2COOCl).
Syntheses of Maleimide Poly(HFPO) Mw ~ 1250 g/mol
Syntheses
To a mixture of oligo(HFPO) methylene alcohol and dry triethy-
lamine (1.5 eq) in dry dichloromethane (DCM), a solution of the
corresponding maleimido acid chloride (1 eq) in dry DCM was
added dropwise. The mixture was then heated under reflux dur-
ing 1 h. The volatiles were then removed under reduced pres-
sure. The product was diluted in 1,1,1,3,3-pentafluorobutane
and washed three times with Deionized (D.I.) water. After the
removal of 1,1,1,3,3-pentafluorobutane, the product was fil-
trated through a 1.2 μm filter frit before photopolymerization.
Synthesis of 4-Maleimidobutyric Acid and
6-Maleimidohexanoic Acid (1a-b)
To a solution of maleic anhydride (2 g) in glacial acetic acid
(15 mL), the corresponding amino acid was added (1 eq). The
mixture was heated to reflux during 3 h. The solvent AcOH
was evaporated via rotary evaporation by using toluene as
azeotropic cosolvent. The crude material was extracted by
using D.I. water (pH ~ 4) and EtOAc. The aqueous phase was
washed two times with EtOAc. The organic phases were com-
bined, dried with MgSO4 and concentrated under vacuum to
afford an orange oil. After drying in vacuum oven, the orange
solids were washed with iced D.I. water (pH ~ 4) and dried in
vacuum oven (70 ꢀC) overnight to provide a whitish powder.
M1 C5 3b (yield = 91%): 1H NMR (400 MHz, C6D6, δ): 1.46
3
(quint, JH-H = 7.4 Hz, N(CH2)2CH2(CH2)2C(O)O , 2H), 1.72
(quint, 3JH-H = 7.4 Hz, NCH2CH2 , 2H), 1.81 (quint, 3JH-H = 7.38 Hz,
3
N(CH2)3CH2CH2C(O)O , 2H), 2.50 (t, JH-H
= 7.4 Hz,
3
CH2CO , 2H), 3.61 (t, JH-H = 7.4 Hz, NCH2 , 2H), 4.79
1
2
3
4-maleimidobutyric acid 1a (yield = 27%): H NMR (400 MHz,
(dd, JH-H = 30.3 Hz, −, JH-F = 12.9 Hz, CF(CF3)CH2O , 1H),
2 3
3
3
CDCl3, δ): 1.92 (quint, JH-H = 7.1 Hz, CH2 , 2H), 2.35 (t, JH-H
= 7.3 Hz, CH2COOH, 2H), 3.52 (t, 3JH-H = 6.9 Hz, NCH2 , 2H),
6.70 (s, CH CH , 2H) 13C NMR (101 MHz, CDCl3, δ):
23.7 ( CH2 ), 31.1 ( CH2COOH), 37.1 ( NCH2 ), 134.3
( CH CH ), 170.9 ( (CO) CH CH (CO) , 177.0 ( COOH).
4.83 (dd, JH-H = 30.3 Hz, −, JH-F = 12.9 Hz, CF(CF3)CH2O ,
1H), 6.90 (s, CH CH , 2H) 13C NMR (101 MHz, C6D6, δ):
23.7 ( C(O)CH2CH2 ), 25.7 ( C(O)CH2CH2CH2 ), 27.9
( NCH2CH2 ), 32.7 ( C(O)CH2), 36.8 ( NCH2 ), 59.0
2
(d, JC-F = 32.7 Hz, CF(CF3)CH2O ), 133.6 ( CH CH ),
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170.0 ( (CO) CH CH (CO) ), 170.6 ( OC(O)
)
19F NMR
N(CH2)8CH2CH2C(O)O , 2H), 2.34 (br, CH2CH2C(O)O , 2H),
3.43 (br, NCH2 , 2H), 4.69 (m, 2JH-H = 31.4 Hz, 3JH-F = 12.8 Hz,
CF(CF3)CH2O , 2H), 6.67 (s, C(O)CH CHC(O) , 2H) 13C NMR
(101 MHz, C6D6, δ): 23.9 (NCH2(CH2) 2CH2CH2C(O)O ), 25.9
( NCH2CH2 ), 28.0 ( N(CH2)2(CH2)CH2 ), 32.8 ( CH2CH2C(O)
(376 MHz, C6D6, δ): = 134.6 RfCF2(CF3)CH2O(CO)Rh, GC–MS,
70 eV, m/z: 41.1 (13), 54.05 (10), 55.1 (24), 68.05 (12), 69.05
(65), 82.05 (18), 83.1 (13), 97.1 (31), 98.05 (26), 110.05
(100), 111.05 (23), 112.1 (12), 147 (14), 150.05 (13),
169 (45), 193.05 (22), 194.05 (54), FTIR (ATR) νmax (cm−1):
827.5–980.3–1119.0–1227.7–1709.8.
2
O ), 37.1 ( NCH2 ), 59.2 (d, JC-F = 30.4 Hz, CF(CF3)CH2O ),
134.0 ( CH CH ), 170.6 ( (CO) CH CH (CO) ), 171.1 ( CF
(CF3)CH2O(CO) ) 19F NMR (376 MHz, C6D6, δ): −134.9
RfCF2(CF3)CH2O(CO)Rh GC–MS, 70 eV, m/z: 54 (10), 55 (12), 69.2
(37), 82.2 (15), 100 (21), 110 (100), 111 (16), 147 (16), 150 (31),
169 (88), 193.1 (15), 194.1 (32), 335.1 (16) MALDI-TOF, [M + Li]+:
1846.6–2012.8–2179.1–2344.3–2510.5 FTIR (ATR) νmax (cm−1):
827.0–978.9–1117.4–1226.9–1711.6.
M1 C10 3c (yield = 95%): 1H NMR (400 MHz, C6D6, δ):
1.45 m, N(CH2)2(CH2)6CH2 , 12H), 1.71 (quint, JH-H
3
=
3
7.2 Hz,
NCH2CH2 , 2H), 1.78 (quint, JH-H = 7.2 Hz,
3
N(CH2)8CH2CH2C(O)O , 2H), 2.48 (t, JH-H
CH2CH2C(O)O , 2H), 3.61 (t, JH-H = 7.2 Hz, NCH2 , 2H),
4.76 (dd, JH-H = 30.3 Hz, JH-F = 12.9 Hz, CF(CF3)CH2O ,
1H), 4.79 (dd, JH-H = 30.3 Hz, JH-F = 12.9 Hz, CF(CF3)
CH2O , 1H), 6.69 (s, CH CH , 2H). 13C NMR (101 MHz,
C6D6, δ): 24.5 ( CH2CH2COO ), 26.7 ( NCH2CH2 ),
28.5–29.2 ( N(CH2)2(CH2)6CH2 ), 29.36 ( CH2CH2COO ),
=
7.2 Hz,
3
2
3
2
3
1
ꢀ
M2 C10 4c (yield = 86%): H NMR (400 MHz, C6D6, 50 C, δ):
1.22 (m, N(CH2)2(CH2)6CH2 , 12H), 1.49 (br, NCH2CH2
,
2H), 1.56 (br, N(CH2)8CH2CH2C(O)O , 2H), 2.29 (br, CH2CH2C
(O)O , 2H), 3.39 (br, NCH2 , 2H), 4.60 (m, 2JH-H = 34.6 Hz, 3JH-
2
29.44 ( NCH2 ), 59.1 (d, JC-F = 32.7 Hz, CF(CF3)CH2O ),
F = 12.3 Hz, CF(CF3)CH2O , 2H), 6.61 (s, CH CH , 2H) 13
C
133.5 ( CH CH ), 170.0 0 ( (CO) CH CH (CO) ), 170.6
(s, OC(O) ). 19F NMR (376 MHz, C6D6, δ): −134.4 RfCF2
(CF3)CH2O(CO)Rh GC–MS, 70 eV, m/z: 41.1 (24), 55.1 (53),
69.05 (82), 81,1 (27), 82.05 (28), 83.1 (40), 97,1 (24), 98.05
(34), 100.05 (18), 110.05 (100), 111.05 (45), 119.05 (13),
147.1 (28), 149.15 (31), 150.05 (14), 169 (45), 191.15 (13),
263.15 (43), 264.15 (89), FTIR (ATR) νmax (cm−1):
827.4–980.7–1119.8–1228.4–1708.8.
NMR (100 MHz, C6D6, δ): 24.5 ( CH2CH2C(O)O ), 26.9
( NCH2CH2 ), 28.7–29.6 ( N(CH2)2(CH2)6CH2 ), 33.0
( CH2CH2COO ), 37.6 ( NCH2 ), 59.2 (d, 2JC-F = 30.5 Hz, CF
(CF3)CH2O ), 134.2 ( CH CH ), 170.7 ( (CO) CH CH
(CO) ), 171.0 ( CF(CF3)CH2O(CO) ) 19F NMR (376 MHz, C6D6,
δ): −135.0 RfCF2(CF3)CH2O(CO)Rh GC–MS, 70 eV, m/z: 54.9 (11),
69 (53), 82 (24), 83.1 (12), 100 (26), 110 (100), 111 (16),
119 (16), 147 (16), 150.1 (32), 169.1 (87), 191.1 (14),
263.1 (30), 264.3 (46), 335 (19) MALDI-TOF, [M + Li]+:
1917.0–2083.2–2249.5–2414.7–2581.0 FTIR (ATR) νmax (cm−1):
826.9–979.1–1117.6–1227.1–1710.6.
Syntheses of Maleimide Poly(HFPO) Mw ~ 2000 g/mol
To a solution of oligo(HFPO) methylene alcohol (Mw = 2000
g/mol, 2 g, 1 mmol), the corresponding maleimide (2 eq) and
DMAP (0.1 eq) in 1,1,1,3,3-pentafluorobutane (15 mꢀL), 2.2 eq
of DCC in DCM (10 mL) were added dropwise at 0 C during
30 min. After 5 min of reaction, the ice bath was removed.
The conversion of the reaction was followed by 19F NMR.
After 30 min, the reaction was stopped. The reaction mixture
was filtrated and concentrated under vacuum. Flash column
chromatography by solid deposit with silica was performed
(15:85 EtOAc:Pentane). The solvents were removed under
vacuum to afford white blurry oils.
RESULTS AND DISCUSSION
Synthesis of the Maleimide PFPAEs
Five different maleimides were synthesized according to
Scheme 2 and their structures are depicted in Figure 1: they
are characterized by PFPAE chains of different lengths
(n = 6.5 for Mx = M1 and n = 11 for Mx = M2) and by a differ-
ent spacer of 3, 5, 10-methylene units ( CH2 unit) between
the fluorinated chain and the maleimide group. The products
will be named Mx C3, Mx C5, Mx C10, respectively.
1
M2 C3 4a (yield = 69%): H NMR (400 MHz, C6D6, δ): 1.81 (br,
The starting materials employed are two different oligo
(HFPO) methylene alcohols Mx having a molecular weights
of 1250 g/mol (n = 6.5) and 2000 g/mol (n = 11) labeled
M1 and M2, respectively. The shortest molecular weight
(i.e. 1250 g/mol) comes from the reduction of Krytox® acyl
fluoride from Chemours Company whereas the longer molecu-
lar weight Krytox® methylene alcohol (i.e. 2000 g/mol) was
directly provided by Chemours Company.
NCH2CH2CH2 , 2H), 2.34 (br, CH2CH2C(O)O , 2H), 3.47
2
3
(br, NCH2 , 2H), 4.66 (m, JH-H = 34.6 Hz, JH-F = 12.1 Hz,
CF(CF3)CH2O , 2H), 6.63 (s, CH CH , 2H) 13C NMR
(101 MHz, C6D6, δ): 22.4 ( NCH2CH2CH2 ), 30.2 ( CH2CH2C
2
(O)O ), 36.4 ( NCH2 ), 59.4 (d, JC-F = 31.4 Hz, CF(CF3)
CH2O ), 134.0 ( CH CH ), 170.7 ( (CO) CH CH (CO) ),
170.8 ( CF(CF3)CH2O(CO) ) 19F NMR (376 MHz, C6D6, δ):
−134.3 RfCF2(CF3)CH2O(CO)Rh GC–MS, 70 eV, m/z: 69.1 (37),
82.1 (15), 100 (14), 110.1 (51), 119 (13), 124.1 (14), 137.1
(16), 138.1 (23), 147 (24), 150 (28), 165.1 (18), 166.1 (76),
169 (100), 335 (18), 528.2 (14) MALDI-TOF, [M + Li]+:
1818.6–1984.8–2151.0–2316.3–2482.5 FTIR (ATR) νmax
(cm−1): 828.0–982.4–1126.3–1232.4–1715.7.
In this work, the synthesis of PFPAEs maleimides was per-
formed via a two-step or three-step reaction. The maleimides
which were used were either commercial products (1c) or
synthesized maleimides (1a-b) (see Experimental section).
Two different esterification methods were then used.
M2 C5 4b (yield = 84%): 1H NMR (400 MHz, C6D6, δ): 1.28 (br,
(CH2)2(CH2)CH2 , 2H), 1.54 (br, NCH2CH2 , 2H), 1.62 (br,
N
Macromonomers 3b-c were efficiently synthesized via nucleo-
philic acyl substitution of the oligo(HFPO) alcohol M1 with
4
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SCHEME 2 Reaction scheme of the addition of maleimide groups to fluorinated oligomers.
methylene alcohol esterification, and this method enabled the
successful synthesis of 4a-c (Route B).35
O
CF3
O
Mx C3
(4a)
N
F
nCF3
CF
O
F
C
C
O
F2
O
According to thermal analysis, the maleimide functionalized
PFPAE macromonomers exhibited improved thermal stability
over the corresponding starting PFPAE alcohol. For example,
Krytox® methylene alcohol Mw ~ 1250 g/mol had a T5% of
122 ꢀC. With the substituents C5 and C10 added to the methy-
lene alcohol, the T5% was increased up to 200 ꢀC for both
products. For Krytox® methylene alcohol Mw ~ 2000 g/mol,
O
CF3
CF
O
N
F
O
Mx C5
(3b & 4b)
F
C
nC
O
O
F2
O
CF3
CF3
CF
O
ꢀ
the T5% was increased from 200 C for the starting alcohol to
F
O
F
C
nC
CF3
O
Mx C10
(3c & 4c)
ꢀ
N
233, 248, and 253 C for M2 C3, M2 C5, and M2 C10 respec-
F2
tively. However, the maleimide was expected to polymerize
before complete degradation explaining the two different
steps by thermogravimetric analyses (TGA). The derivative
highlights the presence of two distinct peaks which means
two steps of degradation (Fig. 2).
O
n=6.5 Mx=M1
n=11 Mx=M2
FIGURE 1 Structures of the different maleimide PFPAEs.
the corresponding acyl chlorides (2b-c; the chlorinated ana-
logues of 1b-c) (Scheme 2, Route A). However, 4a-c (contain-
ing the longer fluorinated chains) did not reach complete
conversion by Route A. Previous work has shown Steglich
esterification to provide a facile route for oligo (HFPO)
In order to determine the phenomena that gave rise to these
two degradation peaks, thermogravimetric analysis coupled
with infrared spectroscopy was used to identify the degrada-
tion products. The information provided by Figure 3 is the
disappearance of the maleimide C C bond (sp2 C H bending)
at 826 cm−1 during the second degradation step. Thus, it
implies that the first degradation pathway was the loss of the
monomer with the presence of a band at 826 cm−1. Next, the
heat transfer from the TGA causes additional polymerization
of the maleimide with no substantial weight loss, and finally
the second degradation is evident as the maleimide polymer
deteriorates.
100
80
60
40
20
0
0
-5
-10
-15
-20
-25
Kinetics Studies of Maleimide PFPAEs
The new maleimides were used as reactive monomers in
photopolymerization. Photopolymerization kinetics were moni-
tored by Real Time-FTIR. The effect of structural parameters
was first studied and discussed depending on their photopoly-
merization kinetics. Then the photopolymerization conditions
such as the presence of air and photoinitiator will be discussed.
25 100 175 250 325 400 475 550
Temperature (°C)
KMA 1250
M1 C5
M2 C3
KMA 2000
M1 C10
M2 C5
M2 C10
Dérivative from M2 C10
FIGURE 2 TGA curves of the starting Krytox® Methylene Alcohol
(KMA) and the monomers M1 C5, M1 C10, M2 C3, M2 C5, and
M2 C10 under nitrogen. [Color figure can be viewed at
wileyonlinelibrary.com]
Influence of the Molecular Weight of the PFPAE
Chain (M1-M2)
For the same hydrogenated spacer C5, two different products
with two PFPAE chains were tested: M1 C5 and M2 C5. The
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segregation and then increase the proximity of the hydroge-
nated maleimides.
Maleimides are known to demonstrate less oxygen inhibition
than (meth)acrylate systems.36 Indeed, both monomers, M1
C5 and M1 C10, achieved complete conversion in the absence
and in the presence of air (Fig. 5). However, oxygen inhibition
was observed. M1 C5 demonstrated a higher oxygen inhibition
as a complete conversion was obtained after more than 400 s
under air. On the contrary, M1 C10 showed a complete con-
version in less than 150 s under air. Consequently, the differ-
ence between both hydrogenated spacers C5 and C10 was
more visible in the presence of air. Moreover, it is notable that
oxygen has greater solubility in organic solvents with longer
aliphatic chains (e.g., heptane and octane), and lower solubil-
ity in those with shorter aliphatic chains (e.g., pentane and
hexane).37 Therefore, the decreased oxygen solubility afforded
by the longer hydrogenated spacer in M1 C10 monomer could
explain this monomer’s greater resistance to oxygen inhibition
and increased reaction rate compared to M1 C5.
FIGURE 3 IR spectra of the degradation products during the first
and second degradation steps.
conversion over time was calculated by measuring the
decrease of the C C band (sp2 C H bending) at 826 cm−1
until quantitative conversion of the products were evident. At
696 cm−1, the C C band loss also confirmed its complete dis-
appearance (see Supporting Information). The higher molecu-
lar weight monomer (M2 C5) reached quantitative conversion
in 10 s, while the lower molecular weight monomer (M1 C5)
reached only 17% conversion in the same period of time
(Fig. 4). Longer UV-curing time was required for M1 C5 to get
to quantitative conversion (70 s). The assumption for the
faster conversion rates is due to the higher percentage of
fluorine. As fluorine content increases, there is larger amount
of submicron segregation between the hydrogenated and fluo-
rinated chains. Thus it promotes the increased probability
of hydrogenated segments encountering each other for
polymerization.
Influence of the Hydrogenated Spacer and Air on
Maleimide Oligo (HFPO) M2
In comparison to the lower molecular weight (M1 products),
the hydrogenated spacer was not a key factor for the reaction
speed for M2 products due to the longer HFPO segment.
Complete conversion was reached after 8 s without air and
after 40 s in the presence of air (Fig. 6). Oxygen inhibition
was observed at the beginning until 10 s and then the reac-
tion speed increased (Fig. 6). Nonetheless, all M2 products
reached quantitative conversion at the same time in compari-
son to M1 products.
Influence of the Hydrogenated Spacer and Air on
Maleimide Oligo(HFPO) M1
Influence of the Presence of Photoinitiator
As mentioned earlier, maleimides can polymerize without
photoinitiators. However, it seems interesting to evaluate the
effect of the photoinitiator on the photopolymerization pro-
cesses without air and M2 C10 was chosen as the reference.
Three different Norrish II-type photoinitiators were used:
BAPO, TPO, and 2-hydroxy-2-methylpropiophenone (Darocur
1173). The photoinitiator efficiency follows this order:
TPO > BAPO > Darocur (Fig. 7). Only TPO permitted faster
photopolymerization kinetics than the maleimide on its own
(Table 1). Having a photoinitiator seemed to increase the
reaction speed during the first seconds but after 80%–90% of
conversion, the reaction speed slowed down. Therefore, the
conversion rates seemed to differ between the reactions with
and without photoinitiators. However, in 15 s, a quantitative
conversion was obtained for the pure M2 C10, TPO, and
BAPO. Darocur 1173 showed the lowest solubility by forming
a gel with M2 C10 which could explain the slower conversion.
When the homopolymerization of the maleimide monomers
M1 C5 and M1 C10 were performed in the absence of air as
shown on Figure 5, both monomers achieved quantitative con-
version by 70 s. They both reached roughly 95% conversion
in 40 s. However, M1 C10 exhibited a greater initial rate of
polymerization than M1 C5, which could be due to the
increased flexibility of the longer hydrogenated spacer C10.
A higher flexibility could help to facilitate the submicron
100
80
60
M1 C5
40
20
0
M2 C5
A cut-off filter was also employed (irradiation area: 400–500 nm)
for some experiments to avoid absorption of light by the mal-
eimide36 and to induce initiation exclusively by the photoini-
tiator. The aim of the filter was to separate the initiating and
the propagation steps. Two initiators were effective in this
zone: BAPO and TPO due to an absorption between 400 and
0
2
4
6
8
10
Time (s)
FIGURE 4 Photopolymerization conversion curves of M1 C5 and
M2 C5 without air.
6
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100
100
80
60
40
20
80
60
M1 C5 air
M1 C5 without air
M1 C10 air
M1 C10 without air
0
40
20
0
0.0
100.0
200.0
Time (s)
300.0
FIGURE 5 Photopolymerization conversion curves for M1 C5 and
M1 C10 with and without air.
0
2
4
6
8
10
500 nm. However, Darocur 1173 does not absorb in this zone.
Consequently, in the presence of a filter, no conversion was
noted for the pure product as well as in the presence of
Darocur 1173 (Table 1). Nonetheless, TPO showed a faster
conversion than BAPO. Moreover, in the presence of a filter,
an inhibition step was detected at the beginning. Therefore,
the initiating step appeared to last 1.5 and 2 s for TPO and
BAPO, respectively, and then the reactions went until com-
plete conversion in 17 s for TPO and in 50 s for BAPO
(Table 1). In any case, the use of photoinitiator was not essen-
tial as the difference between no photoinitiator and TPO is
very slight to reach the quantitative conversion: 8 versus 5 s
in the absence of photoinitiator.
Time (s)
TPO + filter
TPO
BAPO + filter
BAPO
Darocur 1173 + filter
without PI
Darocur 1173
without PI + filter
FIGURE 7 Photopolymerization curves for the use of different
photoinitiators (2% w/w) and a cut-off filter. [Color figure can be
viewed at wileyonlinelibrary.com]
For the highest molecular weight oligo(HFPO) M2 series, the
T5% temperatures were 306 ꢀC, 323 ꢀC and 336 ꢀC for M2
C3, M2 C5 and M2 C10 respectively. The longer the spacer
the higher the T5% as for M1 polymers. All displayed better
thermal stability than their corresponding monomers (Fig. 8).
Thermal and Surface Properties
The starting monomers as well as the cured polymers were
analyzed by TGA and DSC. Contact angle measurements were
also performed by using distilled water and hexadecane.
These degradation temperatures demonstrate a good thermal
resistance in comparison to a previous study about the copol-
ymers (maleate-alt-vinyl ether) PFPAEs.35 The most thermally
stable homopolymer M2 C10 (T10% - 10 K/min: 360 C in N2
and 292 ꢀC in air—Figure 9) showed higher thermal
Thermogravimetric Analyses
The different maleimides were tested by TGA to study their
thermal behavior.
ꢀ
stability than crosslinked PFPAEs with acrylate bonds (T10%
-
The homopolymers M1 C5 and M1 C10 exhibited a T5% of
230 ꢀC and 277 ꢀC respectively. The difference in hydrocarbon
chain lengths clearly showed an improvement for the T5%.
N2 = 256–280 ꢀC).38 They were also comparable to materials
TABLE 1 Table of the Experimental Conditions With and Without
Photoinitiators (2% w/w)
100
Quantitative
Inhibition Conversion
Delay (s) Time (s)
Conversion
Rate at
10 s (%)
80
M2 C5
Sample
60
40
20
0
M2 C5 air
M2 C10
Without PI
Without PI + filter
TPO
>1
–
8
100
0
M2 C10 air
M2 C3
No conversion
>0.5
1.5
>1
2
5
100
97
97.5
83
90
0
M2 C3 air
TPO + filter
BAPO
17
15
0
10
20
Time (s)
30
40
BAPO + filter
Darocur 1173
50
0
130
FIGURE 6 Photopolymerization conversion curves for M2 C3, C5,
and C10 with and without of air. [Color figure can be viewed at
wileyonlinelibrary.com]
Darocur
1173 + filter
–
No conversion
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100
80
60
40
20
0
TABLE 2 Contact Angle Values for Water and Hexadecane
Contact Angle (ꢀ) M1 C5 M1 C10 M2 C3 M2 C5 M2 C10
Water
113
76
117
78
99
66
104
67
124
82
Hexadecane
Contact Angle Measurements
After spin-coating the maleimide PFPAEs onto glass slides and
photopolymerizing them using a conveyor bench, the contact
angles of the products were examined.
25
100 175 250 325 400 475 550
Temperature (°C)
M1 C10 M2 C3 M2 C5
The polymers revealed hydrophobic and oleophobic properties
(Table 2). In this study, the contact angles were dependent on
the chain flexibility afforded by the hydrogenated spacer. The
longer the spacer the better flexibility and consequently,
the better segregation permitted. These attributes lead to
higher contact angle values. It was assumed that the segrega-
tion occurred due to the glass support and altered the contact
angles. It has already been reported for crosslinked methacry-
late PFPAEs with different contact angles between the air
and the glass sides.40,41 Moreover, the values are in good agree-
ment with previous values found for methacrylate PFPAEs
homopolymers42 or crosslinked acrylates PFPAEs.38,43 By using
hexadecane, the same trend was observed: an increase of the
hydrogenated spacer length permitted an increase in contact
angle values. The omniphobic properties were then proved and
the polymers can be used for water–oil repellent applications.
M1 C5
M2 C10
FIGURE
8 TGA curves of polymers after UV-curing under
nitrogen. [Color figure can be viewed at wileyonlinelibrary.com]
based on stronger triazole bonds under air (T10% = 305 and
336 ꢀC) containing PFPAEs and perfluoroalkyl chains.39 How-
ever, the maleimides obviously showed a faster degradation
kinetic in presence of air and seemed to be more sensitive to
oxidation degradation even if these non-crosslinked polymers
provided good results in terms of thermal stability.
DSC Analyses
The glass transition temperatures of the different homopoly-
mers were also studied. They displayed very similar values
from −71 to −66 C for the homopolymers. In any case, only
CONCLUSIONS
ꢀ
the glass transition temperatures of the fluorinated phase
were detected. Indeed, as it is a branched homopolymer con-
taining many fluorinated units for each maleimide unit, it
overlapped the effect of the hydrogenated counterpart
from the maleimide groups. Another observation concerns the
Tmelting for only one of the experimental monomers, M2 C10.
The melting point (Tmelting) for this monomer was −23 ꢀC.
This is due to the long aliphatic chain of C10 and has a compa-
rable melting point to decane, Tmelting = −29.7 ꢀC. However,
surprisingly, no melting temperature was observed for M1
C10 (see Supporting Information).
Maleimide groups bonded to PFPAEs allowed for very rapid
polymerization under UV-light without photoinitiator. The
effect of molecular weight of the oligo(HFPO) was most signifi-
cant. Longer fluorinated chains permitted increased segrega-
tion of the hydrocarbon and fluorocarbon portions of the
polymer. This higher degree of segregation increased the rate
of polymerization. Moreover, the effect of the hydrogenated
spacer was then hidden by the highest molecular weight HFPO
chain. The presence of air showed a slight influence in compar-
ison to some acrylic systems. Indeed, even if oxygen inhibition
was observed at the beginning, complete conversion was easily
obtained. These homopolymers also exhibited excellent ther-
mal and omniphobic properties that are far superior to those
of crosslinked acrylate PFPAE materials previously used in
microfluidics.
100
80
60
ACKNOWLEDGMENTS
Nitrogen - 20 K/min
Nitrogen - 10 K/min
Air - 20K/min
40
20
0
This research project has received funding from the European
Union’s Horizon 2020 Marie Skłodowska-Curie Actions pro-
gram under Grant Agreement No. 690917 – PhotoFluo; Natu-
ral Sciences and Engineering Research Council of Canada
(NSERC), Discovery Grants Program RGPIN-2015-05513, and
Ministère de l’Enseignement Supérieure et de la Recherche.
Air - 10K/min
25
100 175 250 325 400 475 550
Temperature (°C)
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