RAFT polymerization of bromotyramine-based 4-acryloyl-1,2,3-triazole: A functional monomer and polymer family through click chemistry

Article abstract of DOI:10.1039/c5ra27578d

Four new functional acryloyl-triazole monomers derived from bromotyramine were successfully synthesized. These monomers were prepared in an efficient way from organic azides and propargyl acrylate via a copper catalyzed 1,3-dipolar cycloaddition. Polymers containing bromotyramine as a pendant group were obtained via reversible addition-fragmentation chain transfer (RAFT) polymerization. The influence of the chain transfer agent (CTA), solvent, temperature and the length of the linker between the triazole and bromotyramine groups on the polymerization kinetics was studied. It was found that triazoles containing acrylate monomers are characterized by fast polymerization and polymers with controlled molar masses (20 000 g mol^-1) and low dispersities (D_M < 1.5) can be prepared. Glass transition temperatures of these acrylic polymers ranged from 48 °C to 20 °C by controlling the length of the linker between the bromotyramine side groups and the backbone.

Full text of DOI:10.1039/c5ra27578d

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ARTICLE
RAFT polymerization of Bromotyramine-based 4 -acryloyl-1,2,3-
triazole: A Functional Monomers and Polymers Family through
Click Chemistry.
Received 00th January 20xx,
Accepted 00th January 20xx
Sofyane Andjouh,a Christine Bressy,*,a and Yves Blachea
DOI: 10.1039/x0xx00000x
www.rsc.org/
Four new functional acryloyl-triazole monomers derived from bromotyramine were successfully synthesized. These
monomers were prepared in an efficient way from organic azides and propargyl acrylate via a copper catalyzed 1,3-dipolar
cycloaddition. Polymers containing bromotyramine as a pendant group were obtained via the reversible addition-
fragmentation chain transfer (RAFT) polymerization. The influence of the chain transfer agent (CTA), solvent, temperature
and the length of the linker between the triazole and bromotyramine groups on polymerization kinetics was studied. It
was found that triazole containing acrylate monomers are characterized by fast polymerization and polymers with
controlled molar masses (20 000 g.mol-1) and low dispersities (ĐM<1.5) can be prepared. Glass transition temperatures of
these acrylic polymers ranged from 48°C to 20°C by controlling the length of the linker between the bromotyramine side
groups and the backbone.
environmental impacts. Recently, the demand of eco-friendly
antifouling materials has substantially increased and non-toxic
strategies including the incorporation of natural antifouling
1. Introduction
The prevention of biofilm development and the reduction of
surface contamination are important issues in medical
compounds from marine organisms into coatings has been
extensively investigated. 10,34-38
devices 1,2
,
food packaging 3,4
,
shipping 5, aquaculture 6,
Bromotyramine-based compounds e.g. Moloka'iamine
offshore petroleum industry 7... In the literature, antimicrobial
and antibiofilm agents are numerous and large-scale used to
prevent the adhesion of biofilm or to kill microorganisms. The
incorporation of these biocides into coatings was the most
efficient way to protect materials against microorganisms and
inhibit the spread of microbial colonization. 8-11 Any release of
biocidal products from coatings into the surrounding
environment lead to a decrease in efficacy with time. They
were often found to be toxic against non-target species. 12-23
An alternative approach is the design of polymers that can
inhibit biofilm formation thanks to covalently linked biocidal
side groups. This approach avoids any release of biocidal
products and maintains a continious activity. 24 One method of
achieving these polymers is to initially synthesize monomers
containing biocidal moieties and then polymerize them
subsequently or copolymerize them with other co-
monomers.24-29 An alternative method is to chimically modify
existing polymers. 24,30,31 Then, biocidal polymers can be used
as non-releasing coatings active by contact. 32,33 The advantage
of biocidal polymers is justified by the minimization of
41
(A
)
39,40, 3,5-dibromo-4-methoxy-b-phenethylamine (
B
)
and
N-methyl-3-bromotyramine (C) 42 have been reported into the
literature to be efficient antifoulants against several marine
,43
organisms 37,39,42
(Figure 1). Synthetic analogues of this
series of marine compounds were studied in our laboratory
and were shown to display an anti-bacterial activity.
Therefore, polymers containing bromotyramine side groups
could be an alternative approach to develop surfaces which
could inhibit any marine biofilm formation.
The Cu-catalyzed Huisgen 1,3-cycloaddition is one of the
most powerful post functionalization strategy. It has been
combined with great success with controlled polymerization
methods to synthesize
a
wide range of functional
materials. 31,44,45 There are a plethora of examples using the
click chemistry in polymer science. 45-46,47 The development of
this reaction has also contributed to the design of a broad
library of C-vinyl and N-vinyl-1,2,3-triazole based monomers
and their resulting polymers. 48-55 For example, a series of
vinyl-1,2,3-triazole having various substituent groups has been
reported to be successfully employed for the synthesis of
functional polymers and block copolymers using conventional
radical polymerization 55, reversible addition-fragmentation
chain transfer (RAFT) 48,51,52 and nitroxide-mediated
polymerizations. 49,50 Most of triazole containing polymers are
prepared from conventional vinylic monomers. To our
a.Laboratoire Matériaux Polymères-Interfaces-Environnement Marin (MAPIEM),
Université de Toulon, EA 4323, 83957 La Garde, France. E-
mail:christine.bressy@univ-tln.fr; Fax: +33 4 94 14 24 48; Tel:+33 4 94 14 25 80
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
†
DOI: 10.1039/x0xx00000x
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knowledge, no polymers have been prepared directly from were performed on a Viscotek apparatus, compoVsieewdAortficlae OGnPlinCe
acryloyl-1,2,3-triazole monomers via the RAFT process. The Max (comprising a degasser, a pump andDaOnI:a1u0t.1o0s3a9m/Cp5RleAr2)7w57i8tDh
present study aims at preparing a series of 4-acryloyl-1,2,3- a TDA-302 (refractive index detector, right and low angle light
triazole (4-ATri) monomers and their resulting bromotyramine- scattering detector at 670 nm and viscometer) and a UV
containing homopolymers using the RAFT process. These detector ( = 303 nm). The following columns were used: a
polymers will combine the inherent properties of the 1,2,3- Viscotek HHR-H precolumn and two Viscotek ViscoGel
triazole linker group and the active bromotyramine group for GMHHR-H columns. THF was used as the eluent with a flow
further developing anti-adhesive surfaces for marine bacteria. rate of 1 mL.min-1 at 30°C. For each precipitated polymer, the
The general structure of these novel monomers, as well as the refractive index increment (dn/dc) was determined using the
synthetic pathway, are reported in Scheme 1. These OmniSec software, from a solution of known concentration
monomers have been prepared in an efficient way from (ca. 10 mg.mL-1) filtered through a 0.2 µm PTFE filter.
organic azides and propargyl acrylic via copper catalyzed 1,3- The glass transition temperatures (Tg) of the homopolymers
dipolar cycloaddition. The polymerization ability of these were measured with a Q10 differential scanning calorimeter
triazole acrylic monomers has been investigated and kinetics (TA Instruments). The samples were cooled down to -10°C or
has been carried out to point out the controlled character of 0°C and then scanned at a heating rate of 20°C min-1 from -
the polymerization process. Then, the thermal properties of 10°C or 0°C to 140°C. The Tg values were determined as the
the polymers were studied using differential scanning midpoint between the onset and the end of a step transition
calorimetry (DSC) and thermogravimetric analysis (TGA).
on the second heating run using the TA Instruments Universal
Analysis 2000 software.
Thermalgravimetric analysis (TGA) was conducted on a TA
Instruments Q600 using a heating rate of 10°C/min from 300
to 800°C under constant nitrogen flow.
X
NH
R2
R1
O
Typical experimental procedure for the bromination of
Br
methoxybenzene: General procedure for the synthesis of 2a-c.
A : R1 = (CH2)3NH2, R2=H , X=Br
B : R1 =CH3 , R2=H, X=Br
C : R1 = H , R2=CH3, X=H
To a solution of appropriate aromatic halide (1a, 1b, 1c) (1 eq.)
in anhydrous acetonitrile at 0 °C, was added portion wise N-
bromosuccinimide (NBS) (1.5 eq.) under argon atmosphere.
The mixture was stirred at room temperature for 4 h in which
time TLC indicated complete conversion. Solvent was
evaporated under vacuum and the residue was dissolved in
Et2O. The organic layer was washed successively with sat.
Na2CO3, sat. NaCl and H2O. The solvent was dried over Na2SO4
and concentrated under reduced pressure. The residue was
used in the next step without further purification.
Figure 1. Bromotyramine derivatives
2. Experimental section
Materials.
Bromosuccinimide (NBS), sodium carbonate (Na2CO3), sodium
sulfate (Na2SO4), sodium azide (NaN3) N,N-
Anhydrous
acetonitrile
(CH3-CN),
N-
,
dimethylformamide (DMF), dimethyl sulfoxide (DMSO),
dimethyl sulfoxide-d6 (DMSO-d6), N,N-dimethylformamide-d7
(DMF-d7), chloroform-d (CDCl3), methanol, ethyl acetate
(EtOAc), cyclohexane, diethyl ether (Et2O), propargyl acrylate,
Copper(II) sulfate pentahydrate (CuSO4.5H2O), sodium
1. 2-bromo-4-(chloromethyl)-1-methoxybenzene (2a). 2a was
prepared using 1-(chloromethyl)-4-methoxybenzene (1a) (4.7
g, 30 mmol) and NBS (8 g, 45 mmol) in acetonitrile (60 mL). 2a
was obtained as a yellow oily substance (6.68 g, 94.5%).
4
1H NMR (400 MHz, CDCl3) δ 7.58 (d, J = 2.2 Hz, 1H, C-HAr.),
ascorbate,
1-(chloromethyl)-4-methoxybenzene,
1-(3-
7.30 (dd, 3J = 8.4, 4J =2.2 Hz, 1H, C-HAr), 6.87 (d, 3J = 8.4 Hz, 1H,
C-HAr), 4.52 (s, 2H, CH2-Cl), 3.90 (s, 3H, CH3-O).
bromopropyl)-4-methoxybenzene
and
4-methoxybenzyl
chloride were purchased from Aldrich and used as received. 1-
(2-Chloroethyl)-4-methoxybenzene was purchased from
ACROS. Cyanomethyl dodecyl trithiocarbonate (CMDT) and 2-
13C NMR (100 MHz, CDCl3) δ 155.5(CAr-OCH3), 133.2 (CHAr),
130.6(CAr), 128.7(CHAr), 111.5(CHAr), 111.2(CBrAr-OCH3),
55.9(CH3-O), 45.0 (CH2-Cl).
(dodecylthiocarbonothioylthio)-2-methylpropionic
acid
(DDMAT) were used as chain transfer agents (Aldrich).
Azobis(isobutyronitrile) (AIBN, Aldrich) was recrystallized from
methanol prior to be used.
2. 2-bromo-4-(2-chloroethyl)-1-methoxybenzene (2b). 2b was
prepared using 1-(2-chloroethyl)-4-methoxybenzene (1b) (6.82
g, 40 mmol) and NBS (10.68 g, 60 mmol) in acetonitrile (80
mL). 2b was obtained as a yellow oily substance (9.9 g, 99%).
1H NMR (400 MHz, CDCl3) δ 7.41 (d, 4J = 2.2 Hz, 1H, C-HAr), 7.13
Characterizations. 1H- (400 MHz) and 13C- (100 MHz) NMR
spectra were recorded on
a Brucker Advance NMR
3
4
3
spectrometer. Mass spectra were measured on an ion trap
mass spectrometer fitted with an ESI interface (Esquire 6000,
Bruker Daltonics).The number-average molar mass (Mn) and
dispersity (ĐM) of polymers were determined by triple
detection size exclusion chromatography (TD-SEC). Analyses
(dd, J = 8.4, J =2.2 Hz, 1H, C-HAr), 6.85 (d, J = 8.4 Hz, 1H, C-
3
HAr), 3.88 (s, 3H, CH3-O), 3.67 (t, J = 7.3 Hz, 2H, CH2-CH2-Cl),
2.98 (t, 3J = 7.3 Hz, 2H, CH2-CH2-Cl).
2 | RSC Adv., 20xx, 00, 1-3
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13C NMR (100 MHz, CDCl3) δ 154.1(CAr-OCH3), 132.8(CHAr), mmol) in N,N-Dimethylformamide (60 ml). 3c was obtained as
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DOI: 10.1039/C5RA27578D
131.0(CAr), 128.4(CHAr), 111.3(CHAr), 110.8 (C-BrAr), 55.6(CH3- yellow oil (5.06 g, 95%).
O), 44.5(CH2-CH2-Cl), 37.1(CH2-CH2-Cl).
1H NMR (400 MHz, CDCl3) δ 7.16 (m, 2H, 2 C-HAr), 6.89 (m, 2H,
2 C-HAr), 3.81 (s, 3H, CH3-O), 3.48 (t, J = 7.2 Hz, 2H, CH2-CH2-
(2c). 2c N3), 2.86 (t, J = 7.2 Hz, 2H, CH2-CH2- N3).
3. 2-bromo-4-(3-bromopropyl)-1-methoxybenzene
was prepared using 1-(chloromethyl)-4-methoxybenzene (1c
)
13C NMR (100 MHz, CDCl3) δ 158.5(CAr-OCH3), 130.0(CAr), 129.7
(3.44 g, 15 mmol) and NBS (4 g, 22.5 mmol) in acetonitrile (30 (2 CHAr), 114.1 (2 CHAr), 55.2(CH3-O), 52.7(CH2-CH2-N3),
mL). 2c was obtained as a dark brown oily substance (4.58 g, 34.5(CH2-CH2-N3).
99%).
1H NMR (400 MHz, CDCl3) δ 7.39 (d, J = 2.2 Hz, 1H, C-HAr),
IR (thin film) 
N3 2090 cm−1.
4
7.11 (dd, 3J = 8.4, 4J =2.2 Hz, 1H, C-HAr), 6.84 (d, 3J = 8.4 Hz, 1H, 7. 4-(3-azidopropyl)-2-bromo-1-methoxybenzene
(3d). 3d was
C-HAr), 3.88 (s, 3H, CH3-O), 3.38 (t, 3J = 6.5 Hz, 2H, CH2-Br), 2.71 prepared using 2c (4 g, 13 mmol) and sodium azide (NaN3) (2.2
(t, J = 7.3 Hz, 2H, CH2-CH2-CH2-Br), 2.13 (m, 2H, CH2-CH2-CH2- g, 33.8 mmol) in N,N-dimethylformamide (30 mL). 3d was
Br).
obtained as dark brown oil (3.32 g, 94.5%).
4
13C NMR (100 MHz, CDCl3) δ 154.0(CAr-OCH3), 133.8 (CAr), 1H NMR (400 MHz, CDCl3) δ 7.37 (d, J = 2.2 Hz, 1H, C-HAr),
132.9(CHAr), 128.3(CHAr), 111.7(CHAr), 111.2(C-BrAr), 56.0(CH3- 7.08 (dd, 3J = 8.4, 4J =2.2 Hz, 1H, C-HAr), 6.83 (d, 3J = 8.4 Hz, 1H,
O), 33.8(CH2-CH2-CH2-Br), 32.8(CH2-CH2-CH2-Br), 32.4(CH2-CH2- C-HAr), 3.87 (s, 3H, CH3-O), 3.28 (t, J = 6.7 Hz, 2H, CH2-CH2-CH2-
CH2-Br).
N3), 2.62 (t, J = 7.7 Hz, 2H, CH2-CH2-CH2-N3), 1.87 (m, 2H, CH2-
CH2-CH2-N3).
General Procedure for the synthesis of azides 3a-d.
13C NMR (100 MHz, CDCl3) δ 154.0(CAr-OCH3), 134.2(CAr),
A mixture of appropriate halide (1 equiv) and sodium azide 132.8(CHAr), 128.2(CHAr), 111.8(CHAr), 111.3(CBrAr), 55.9(CH3-
(NaN3) (2.6 equiv) in N,N-dimethylformamide (DMF) was O), 50.2(CH2-CH2-CH2-N3), 31.2(CH2-CH2-CH2-N3), 30.2(CH2-CH2-
stirred for 5 h at 90 °C. The reaction temperature was allowed CH2-N3).
to warm to room temperature and the reaction mixture was IR (thin film)
diluted with Et2O. The organic phase was washed with brine

N3 2090 cm−1.
and water, dried over Na2SO4, and concentrated under Typical method for preparation of monomers
vacuum. The azide products were directly used for the next An appropriate azide (1 equiv.) and propargyl acrylate (1.5
reaction without further purification.
equiv.) were dissolved in a 1:2 mixture of water and ethanol.
To the solution was added CuSO4.5H2O (0.04 equiv) and
4. 4-(azidomethyl)-2-bromo-1-methoxybenzene
(3a). 3a was sodium ascorbate (0.08 equiv). The resultant mixture was
prepared using 2a (5.89 g, 25 mmol) and sodium azide (NaN3) stirred at room temperature for 12 h at which time TLC
(4.22 g, 65 mmol) in N,N-dimethylformamide (50 mL). 3a was revealed complete conversion. The reaction solution was
obtained as dark brown oil (5.99 g, 99%).
diluted with brine and extracted three times with EtOAc. The
4
1H NMR (400 MHz, CDCl3) δ 7.51 (d, J = 2.2 Hz, 1H, C-HAr), organic layers were washed with water, dried over Na2SO4 and
7.23 (dd, 3J = 8.4, 4J =2.2 Hz, 1H, C-HAr), 6.90 (d, 3J = 8.4 Hz, 1H, evaporated under vacuum. Crude triazoles were purified by
C-HAr), 4.26 (s, 2H, CH2-N3), 3.90 (s, 3H, CH3-O).
silica gel column chromatography using a mixture of
13C NMR (100 MHz, CDCl3) δ 155.2(CAr-OCH3), 132.5(CHAr), EtOAc/cyclohexane (70/30) as mobile phase.
128.4(CAr), 128.0(CHAr), 111.4(CHAr), 111.1(C-BrAr), 55.5(CH3-O),
52.9(CH2-N3).
8. (1-(3-bromo-4-methoxybenzyl)-1H-1,2,3-triazol-4-yl)methyl
acrylate 4-ATri4a). 4-ATri4a was obtained from azide 3a (4.84
g, 20 mmol) and methyl propiolate (3.3 g, 30 mmol) as white
3b). 3b was solid (6.78 g, 96%).
prepared using 2b (8.98 g, 36 mmol) and sodium azide (NaN3) 1H NMR (400 MHz, CDCl3) δ 7.56 (s, 1H, C-Htr.), 7.41 (d, J = 2.2
IR (thin film)

N3 2092 cm−1.
(
5. 4-(2-azidoethyl)-2-bromo-1-methoxybenzene
(
4
3
4
(6.09 g, 93.6 mmol) in N,N-dimethylformamide (70 mL). 3b Hz, 1H, C-HAr), 7.14 (dd, J = 8.4, J =2.2 Hz, 1H, C-HAr), 6.79 (d,
was obtained as dark brown oil (8.8 g, 95.5%).
3J = 8.4 Hz, 1H, C-HAr), 6.30 (dd, 3J = 17.3, 2J =1.4 Hz, 1H,
1H NMR (400 MHz, CDCl3) δ 7.40 (d, 4J = 2.2 Hz, 1H, C-HAr), 7.12 CH=CHHE), 6.00 (dd, J = 17.3, J =10.4 Hz, 1H, CH=CH2), 5.73
3
3
3
4
3
(dd, J = 8.4, J =2.2 Hz, 1H, C-HAr), 6.85 (d, J = 8.4 Hz, 1H, C- (dd, 3J = 10.4, 2J 1.4 Hz, 1H, CH=CHHZ), 5.35 (s, 2H, CH2-N), 5.17
3
HAr), 3.88 (s, 3H, CH3-O), 3.47 (t, J = 7.1 Hz, 2H, CH2-CH2-N3), (s, 2H CH2-O-C=O), 3.77 (s, 3H, CH3-O).
2.80 (t, 3J = 7.1 Hz, 2H, CH2-CH2-N3).
13C NMR (101 MHz, CDCl3) δ 165.7(C=O), 156.0(CAr-OMe),
13C NMR (100 MHz, CDCl3) δ 154.7(CAr-OCH3), 133.4(CHAr), 143.0(Ctr), 133.0 (CHAr), 131.4(CH=CH2), 128.5(CHAr), 127.8
131.6(CAr), 128.8(CHAr), 111.9(CHAr), 111.5(C-BrAr), 56.2(CH3-O), (CAr), 127.8(CH=CH2), 123.6 (CHtr), 112.1(CHAr), 111.9(CBrAr),
52.33(CH2-CH2-N3), 34.04(CH2-CH2-N3).
57.5 (CH3-O), 56.2(CH2-O-C=O), 52.8(CH2-N).
M.p. = 99-100°C. (ESI, m/z) 352.05 ([M+H,]+, 79Br) 354.02
([M+H+2]+, 81Br).
IR (thin film)

N3 2090 cm−1.
6. 1-(2-azidoethyl)-4-methoxybenzene (3c). 3c was prepared
using 1b (5.1 g, 30 mmol) and sodium azide (NaN3) (5.07 g, 78 9.
(1-(3-bromo-4-methoxyphenethyl)-1H-1,2,3-triazol-4-
yl)methyl acrylate
(4-ATri4b). 4-ATri 4b was obtained from
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th
azide 3b (8.45 g, 33 mmol) and propargyl acrylate (5.45 g, 49.5 account a full conversion of monomers and Mn , VcieawlcAurtliaclteeOdnlianes
DOI: 10.1039/C5RA27578D
mmol) as white solid (11.7 g, 97%).
follows (Eqn.1):
4
1H NMR (400 MHz, CDCl3) δ 7.41 (s, 1H, C-Htr), 7.14 (d, J = 2.1
3
4
Hz, 1H, C-HAr), 6.83 (dd, J = 8.4, J =2.1 Hz, 1H, C-HAr), 6.66 (d,
(1)
3J = 8.4 Hz, 1H, C-HAr), 6.26 (dd, 3J = 17.3, 2J =1.4 Hz, 1H,
3
CH=CHHE), 5.97 (dd, J = 17.3, 10.4 Hz, 1H, CH=CH2), 5.70 (dd,
Where [M]0 and [CTA]0 are the initial concentrations of
monomer and CTA respectively, Mmonomer and MCTA are the
molar mass of monomer and CTA respectively, and conv. is the
monomer conversion.
2
3J = 10.4, J =1.4 Hz, 1H, CH=CHHZ), 5.12 (s, 2H, CH2-O-C=O),
4.42 (t, J = 7.2 Hz, 2H, CH2-CH2-N), 3.69 (s, 3H, CH3-O), 2.99 (t, J
= 7.2 Hz, 2H, CH2-CH2-N).
13C NMR (101 MHz, CDCl3) δ 165.5(C=O), 154.6(CAr-OMe),
142.1(Ctr), 133.0(CHAr), 131.2(CH=CH2), 130.2(CHAr), 128.5(CAr),
All polymerizations were carried out in
a
high
pressure/vacuum Wilmad NMR tube. representative
A
127.7(CH=CH2),
124.0(CHtr),
111.8(CHAr),
111.3(CBrAr),
example is as follows: 4-ATri 4b (137 mg, 0,375 mmol),
cyanomethyl dodecyl trithiocarbonate (CMDT) (2.2 mg, 0.007
mmol), AIBN (0.114 mg, 0.0007 mmol), and DMSO-d6 (0.25 mL)
were placed in a dry high pressure/vacuum Wilmad NMR tube
and then the solution was degassed by three freeze-evacuate-
thaw cycles. The polymerization occurred into the NMR
apparatus, heated at 60°C during 15h, and followed by 1H NMR
analysis at regular times. After cooling down to room
temperature, the crude sample was dissolved in a small
amount of DMSO, purified by reprecipitation into a large
excess of methanol, and the resulting product was dried under
vacuum at room temperature (84 mg, yield 62 %).
57.3(CH3-O), 55.9(CH2-O-C=O), 51.2(CH2-CH2-N), 35.0(CH2-CH2-
N).
M.p. = 69-70°C. (ESI, m/z) 366.05 ([M+H]+, 79Br) 368.06
([M+H+2]+, 81Br).
10.
acrylate
(1-(4-methoxyphenethyl)-1H-1,2,3-triazol-4-yl)methyl
4-ATri 4c). 4-ATri 4c was obtained from azide 3c (4.78
(
g, 27 mmol) and propargyl acrylate (4.46 g, 40.5 mmol) as
white solid (7.39 g, 95%).
1H NMR (400 MHz, CDCl3) δ 7.35 (s, 1H, C-Htr), 6.97 – 6.87 (m,
2H, 2C-HAr), 6.78 – 6.68 (m, 2H, 2C-HAr), 6.33 (dd, 3J = 17.3, 2J =
1.4 Hz, 1H, CH=CHHE), 6.03 (dd, 3J = 17.3, 10.4 Hz, 1H, CH=CH2),
3
2
5.76 (dd, J = 10.4, J = 1.4 Hz, 1H CH=CHHZ), 5.18 (s, 2H, CH2-
O-C=O), 4.46 (t, J = 7.3 Hz, 2H, CH2-CH2-N), 3.69 (s, 3H, CH3-O),
3.06 (t, J = 7.3 Hz, 2H, CH2-CH2-N).
1
The conversion of 4-ATri 4b is determined from in situ H
NMR analysis of the reaction mixture by comparing the
integration (IH) area of peaks at 6.10-6.20 ppm (one vinylic
proton of monomer) and the peak at 7.90-8.06 ppm
13C NMR (101 MHz, CDCl3) δ 165.7(C=O), 158.5(CAr-OMe),
142.2(Ctr), 131.2(CH=CH2), 129.5 (2 CHAr), 128.7(CAr),
127.8(CH=CH2), 124.1(CHtr), 114.0 (2 CHAr), 57.5(CH3-O),
55.0(CH2-O-C=O), 51.7(CH2-CH2-N), 35.7(CH2-CH2-N).
M.p. = 42-43°C. (ESI, m/z) 288.11 [M+H]+.
corresponding to the triazole proton of both monomer and
NMR
polymer. The conversion of 4-ATri 4b and Mn
were
determined with time as follows (Eqn.2 and 3):
(2)
11. (1-(3-(3-bromo-4-methoxyphenyl)propyl)-1H-1,2,3-triazol-
4-yl)methyl acrylate (4-ATri 4d). 4-ATri 4d was obtained from
azide 3d (3.24 g, 12 mmol) and propargyl acrylate (1.98 g, 18
with,
mmol) as yellow oil (4.38 g, 96%).
IH, polymer = IH, 7.90-8.06 ppm – IH, 6.10-6.20 ppm
IH(monomer + polymer) = IH, 7.90-8.06 ppm
4
1H NMR (400 MHz, CDCl3) δ 7.58 (s, 1H, C-Htr), 7.28 (d, J = 2.2
Hz, 1H, C-HAr), 7.00 (dd, J = 8.4, 4J = 2.2 Hz, 1H, C-HAr), 6.77 (d,
3J = 8.4 Hz, 1H, C-HAr), 6.36 (dd, 3J = 17.3, 2J = 1.4 Hz, 1H,
end
3
CH=CHHE), 6.06 (dd, J = 17.3, 10.4 Hz, 1H, CH=CH2), 5.79 (dd,
(3)
2
3J = 10.4, J = 1.4 Hz, 1H, CH=CHHZ), 5.24 (s, 2H, CH2-O-C=O),
4.28 (t, J = 7.1 Hz, 2H, CH2-CH2-CH2-N), 3.79 (s, 3H, CH3-O), 2.51
(t, J = 7.5 Hz, 2H, CH2-CH2-CH2-N), 2.22 – 2.07 (m, 2H, CH2-CH2-
CH2-N).
where Mmonomer and MCTA are the molar mass of monomer
and CTA respectively, and
is the
c ain end
concentration of CTA converted into macro-CTA with time.
13C NMR (101 MHz, CDCl3) δ 165.9(C=O), 154.3(CAr-OMe),
142.7(Ctr), 133.6(CHAr), 133.0(CH=CH2), 131.5(CHAr), 128.4(CAr),
c ain end (t)
The conversion of macro-CTA
(
) is
determined from in situ 1H NMR analysis of the reaction
mixture by comparing the integration (IH) area of peaks at 4.4
ppm corresponding to two protons of unconsumed CTA (CH3-
(CH2)11-S-(C=S)-S-CH2-CN) and the peak at 0.85 ppm
corresponding to the three protons (CH3-(CH2)11-S-(C=S)-S-CH2-
CN) of both unconsumed CTA and consumed CTA, as follows
(Eqn.4):
127.9(CH=CH2),
123.8(CHtr),
112.0(CHAr),
111.5(CBrAr),
57.6(CH3-O), 56.2(CH2-O-C=O), 49.3(CH2-CH2-CH2-N), 31.5(CH2-
CH2-CH2-N), 31.1(CH2-CH2-CH2-N). (ESI, m/z) 380.06 ([M+H]+,
79Br) 382.06 ([M+H+2]+, 79Br).
General Procedure for RAFT Polymerization
1
In situ H NMR RAFT polymerizations were carried out using
CMDT or DDMAT as CTAs and AIBN as initiator at a molar ratio
[CTA]/[AIBN]=10. The concentration of CTA was adjusted to
the targeted number-average molar mass (Mntarget), taking into
(4)
c ain end
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with N-bromosuccinimide (NBS) in anhydrousVieawcAerttioclenOitnrliinlee
The final molar mass (MnNMR) of the polymer is also affording brominated derivatives 2a-cDOinI: 10e.1x0c3e9l/lCen5RtA2y7i5e7l8dDs
determined after precipitation in methanol as follows (Eqn.5):
(>90%). Then, compounds 1b and 2a-c were treated with
sodium azide in dimethylformamide leading to the
corresponding azides 3a-d. Theses azides with different length
of the methylene spacer between the aromatic ring and azide
(5)
where Xn is the number of repeating unit. Xn is determined group were obtained with excellent yields (>90%) and did not
1
from H NMR spectra of the purified polymer (Figures 1-3 in require any purification.
electronic supplementary information†) by comparing the
The synthesis of the targeted acrylic monomers (4a-d) was
integration (IH) area of peaks at 3.80 ppm (methoxy protons then achieved by performing the copper-catalyzed 1,3-dipolar
(3H) of polymer) and the peak at 0.85 ppm corresponding to cycloaddition of the organic azides with propargyl acrylate. In
three protons of CTA inserted at the end of the polymer chains general, this reaction usually proceeds to completion in 6–36 h
(Eqn.6).
at room temperature in water with a variety of organic co-
solvents, such as tert-butanol, ethanol, DMF, DMSO, THF, or
CH3CN. This reaction is used for a wide class of azides and
alkynes.56 Ethanol was chosen rather than DMF to allow an
easier workup and a better purity of products as reported in
our previous work.57 In practice, propargyl acrylate was added
(6)
3. Results and Discussion
Synthesis of monomers
The synthesis of monomers 4a-d is outlined in Scheme 1.
The aryl azide intermediates were synthesized from
commercially available benzyl halides (1a-c) as shown in
to
a solution of the appropriate azide (3a-d) with
CuSO4/sodium ascorbate in water/ethanol mixture (50/50). A
reaction time of 12h was optimized at room temperature.
Scheme 1. Briefly, each derivative (1a-c) was first brominated
( )
( )
n
n
X
X
NBS(1.5eq.) / CH3-CN
0°C,1h
Me
Me
O
O
Br
1a n=1 X=Cl
1b n=2 X=Cl
1c n=3 X= Br
2a n=1 95%
2b n=2 99%
2c n=3 99%
NaN3 / DMF
5h, 90°C
( )
( )
n
n N3
X
NaN3/DMF
5h, 90°C
Me
Me
O
O
R
1b n=2
3a n=1 R=Br 99%
3b n=2 R=Br 95%
3c n=2 R=H 95%
3d n=3 R=Br 94%
S
S
NC
CH2(CH2)10CH3
O
O
S
O
N
( )
O
n
N
N
CuSO4 /
NaAsc
n
Me
O
N
O
S
S
CN
EtOH/H2O(2/1)
12h, rt
H3C(H2C)10H2C
R
N
S
N
O
( )
4-ATri 4a n=1 R=Br 96%
4-ATri 4b n=2 R=Br 97%
4-ATri 4c n=2 R=H 95%
4-ATri 4d n=3 R=Br 96%
AIBN, DMSO-d6 or DMF-d4
n
O
Br
p(4-ATri 4a-d)
Scheme 1. Synthetic pathways for triazole acrylate monomers and polymers.
RAFT polymerization of monomers (4-ATri 4a-d)
The RAFT polymerization was selected because it can be used
with a wide range of monomers and reaction conditions, and
The aim of this study was to demonstrate that the RAFT in each case it provides polymers with controlled molar masses
polymerization of these triazole containing monomers follows with narrow molar mass distributions.58 Furthermore, the
a controlled process. Herein, we first demonstrate the atom transfer radical polymerization (ATRP) of a 4-acryloyl
controlled character of the RAFT polymerization of 4-acryloyl- 1,2,3-triazole monomer (ferrocenylmethyl triazole methyl
1-bromotyramine-1,2,3-triazole monomer (4-ATri 4b) which is acrylate) has initially failed.59
the direct analogue of natural bromotyramines (Scheme 1).
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First, kinetics was investigated by using conventional free
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The homopolymerizations were first carried out with CMDT
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DOI: 10.1039/C5RA27578D
radical polymerization (Table 1, Entry Nr. 1). The monomer 4- in DMSO-d6 or DMF-d7 at a molar ratio [CTA]/[AIBN] of 10/1 at
ATri 4b was successfully polymerized reaching 96 % of different temperatures. Whatever the conditions used, the
conversion and leading to a polymer with a high molar mass targeted molar mass was 20 000 g.mol-1. The results are
TD-SEC
(Mn
= 269 600 g.mol-1) and a high dispersity (ĐM = 3.8). 4- summarized in Table 1 (Entries Nr. 2 to 8). Polymerizations
ATri 4b was further homopolymerized via the RAFT process to carried out at low temperatures (40 and 50°C) failed because
control the growth of polymer chains using two different few amounts of radicals were generated at these lower
CTAs. 60-62 The reactivity of the RAFT agent has to be adjusted temperatures. In addition, any impurities in monomer, RAFT
to the reactivity of the monomer to obtain good control over agent or solvent could inhibit the polymerization (Entries 2 and
time while retaining an ideally unaltered rate of 3, respectively). At 60°C, the disappearance of the vinyl
polymerization. The reactivity of a RAFT agent is governed by protons from the acrylate group, around 5.6-6.4 ppm, and the
its R and Z groups. Scheme 2 shows the RAFT agents selected appearance of broad peaks assigned to the main chain around
in our study.
1.2-2.5 ppm (-CH2-) suggested the successful polymerization
for 4-ATri 4b monomers (Figure 2).
S
S
CN
S
S
COOH
S
S
Cyanomethyl dodecyl trithiocarbonate (CMDT)
2-(Dodecylthiocarbonothioylthio)-2-methylpropionic acid (DDMAT)
Scheme 2. RAFT agents employed in the controlled radical polymerization of 4-ATri 4b.
8
4
10
7
9
N
O
N
N
5
6
2
5
O
8
3
1
1
6
7
10
9
10
4
3
O
2
Br
a
b
CN
4
10
9
N
O
N
N
S
n
5
2
O
8
1
S
S
11
6
7
4
3
CH2(CH2)10CH3
O
5
6
11
Br
3
8
7
2
1
9,10
c
Figure 2. 1H-NMR spectra of (a) 4-ATri 4b in CDCl3, (b) its homopolymer poly(4-ATri 4b) after 15h of reaction in DMSO-d6 at 60°C,
and (c) the purified polymer in CDCl3
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High monomer conversion values were obtained at 60 °C. steric effect of the bromine atom. Figure 3 also shows that the
The resulting poly(4-ATri 4b) exhibited a low dispersity value length of the linker between the triazole function and the
and the awaited Mn value (Entry 4, Table 1). An increase of the aromatic ring affects the polymerization rate of monomers.
reaction temperature to 70°C led to faster kinetics with 86 % Increasing the methylene spacer from one carbon (4-ATri 4a
)
of conversion after 1h30mn while the polymerization reached to two carbon atoms (4-ATri 4b) led to a decrease in
83 % of conversion after 5h at 60°C (electronic supplementary polymerization rate. The increase of the length of the alkyl
information†, Figure 4). Nevertheless, polymers with lower Mn spacer should pull away the aromatic ring from the polymer
TD-SEC
values (Mn
= 8 600 g.mol-1) than the targeted ones were backbone reducing any steric effect or electronic effect of the
bromotyramine moiety on the polymerization rate.
obtained at 70°C. In addition, the resulting poly(4-ATri 4b
)
showed a TD-SEC peak with a broad molar mass distribution Surprisingly, the polymerisation rate of 4-ATri 4d (with three
(ĐM = 2.9). This result suggests that side reactions or methylene groups) is higher than the one for 4-ATri 4b (with
termination steps could occur resulting in low molar mass and two methylene groups) which is slightly lower than the one
high dispersity values at 70°C.
found for 4-ATri 4a (with one methylene group). The origin of
Similar kinetics was obtained in DMSO-d6 and in DMF-d7, the slow polymerization kinetics of 4-ATri 4b comparing to the
whatever the reaction temperature (Figure 4 in electronic two other monomers was not investigated herein.
supplementary information†). Polymers with lower dispersities
were prepared at 60°C in both solvents (Table 1, Entries 4 and 4b, Mn
In a representative plot of RAFT polymerization of 4-ATri
NMR
(t) increased linearly with monomer conversion,
6). The substitution of CMDT by DDMAT led to a slight increase further confirming the controlled behavior of the
of the dispersity value from 1.3 to 1.5 (Table 1, entries 6 and 8, polymerization process (Figure 4). All other polymers showed
NMR
Figure 5 in electronic supplementary information†).
similar linear relationship of Mn
(t) with monomer
The linear semilogarithmic plots shown in Figure
3
conversion (electronic supplementary information†, Figure 7-
demonstrate a control of the growth of the polymer chains 9). The final values of Mn were consistent with the expected
with time. The non-brominated monomer (4-ATri 4c) showed a ones with narrow molar mass distribution excepting for the
TD-
higher reactivity than the brominated one (4-ATri 4b). The one-carbon linker monomer (4-ATri 4a) where a higher Mn
lower reactivity of 4-Tri-4b might result from a poorer SEC was obtained (Table 2).
solubility of this monomer relative to 4Tri-4c and from the
Table 1. Experimental conditions for the RAFT polymerization of 4-ATri 4b using AIBN as initiator. Mn, and ĐM values obtained after 15 h of
reaction.
th(c)
TD-SEC(d)
T
(°C)
Conv(a)
(%)
Yield(b)
(%)
Mn
Mn
(e)
Entry
CTA
solvent
ĐM
dn/dc(f)
0.069
(g.mol-1)
(g.mol-1)
1
2
3
4
5
6
7
8
-
70
40
50
60
70
60
70
60
DMSO
DMSO
DMSO
DMSO
DMSO
DMF
96
69
-
g
269 600
3.8
g
g
g
g
g
g
CMDT
CMDT
CMDT
CMDT
CMDT
CMDT
DDMAT
-
-
-
-
-
-
-
g
g
g
g
g
-
-
-
-
-
97
99
95
97
98
62
53
48
42
45
19 503
19 834
19 000
19 474
19 495
22 100
8 600
1.3
2.9
1.5
2.7
1.5
0.111
0.112
0.099
0.118
0.104
23 700
7 170
DMF
DMSO
18 900
a Monomer conversion determined by 1H NMR (calculated from Eqn. 2) at 15 h of reaction.
b Yield determined gravimetrically.
c Calculated from Eqn. 1.
d Number-average molar mass obtained from TD-SEC.
e ĐM = Mw/Mn obtained from TD-SEC.
f Assessed by TD-SEC.
g No polymer obtained.
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3,5
3
20 000
18 000
16 000
14 000
12 000
10 000
8 000
6 000
4 000
2 000
0
2,5
2
1,5
1
0,5
0
0
50
100
150
200
250
300
0
20
40
60
80
100
Time (mn)
Monomer conversion (%)
Figure 3. Ln([M]0/[M]) vs time. Homopolymerizations of
triazole acrylates in DMSO-d6 at 60°C. CMDT/AIBN molar ratio
Figure 4. Evolution of MnNMR (t) vs monomer conversion during
the RAFT polymerization of a representative monomer 4-ATri
of 10/1. 4-ATri 4a
4d ).
(▲), 4-ATri 4b (■), 4-ATri 4c (o) and 4-ATri
4b (■) in DMSO-d6 at 60°C. Monomer/CDMT/AIBN molar ratio
(

of 1.5/10/1. Mnth=20 000 g.mol-1. The solid line is the linear fit
to the data. The dashed line is corresponding to the theoretical
line.
Thermal properties
significant influence of the sterically hindered bromine atom
on the mobility of the polymer main chain. This is in
agreement with the previous behavior shown during the
The thermal properties of the homopolymers were
characterized by DSC. Thermal properties of homopolymers
exhibited a strong relationship with length of the linker.
As s own in electronic supplementary information†(Figure 10),
4-ATri-4d, which contains the longest linker, showed the
lowest Tg around 20°C, whereas 4-ATri 4b and 4-ATri 4a with
shorter linkers exhibited Tg at 42 and 48°C, respectively.
Clearly, the Tg value of homopolymers decreases with
increasing the length of the linker between the bulky aromatic
ring and the polymer backbone. The non-brominated
monomer (4-ATri 4c) showed lower Tg (Tg = 34°C) than the
brominated one (4-ATri 4b). This result demonstrates the
polymerization.
The thermal
degradation of
the
homopolymers was studied by TGA (electronic supplementary
information†, Figures 11 and 12). It was found that in inert
atmosphere they all decompose in one major step, excepting
the non-brominated one, with a maximum temperature
around 320-330°C leaving a residue (char) which is thermally
quite stable, decomposing at a low rate at higher temperature.
The first degradation step (100-200°C) is assigned to the
thermal decomposition of trithiocarbonate moieties, as
previously reported.63
Table 2. Results for the RAFT polymerization of 4-ATri 4 a-d at T = 60°C, in DMSO-d6 after 15h of reaction. Monomer/CMDT/AIBN molar
ratio: 1.5/10/1.
th(c)
NMR(d)
TD-SEC(e)
Conv(a)
(%)
Yield(b)
(%)
Mn
Mn
Mn
(f)
Monomer
ĐM
dn/dc(g)
(g.mol-1)
(g.mol-1)
(g.mol-1)
4-ATri 4a
4-ATri 4b
4-ATri 4c
4-ATri 4d
97
97
97
98
38
62
36
47
19 482
19 503
19 513
19 598
34 110
22 290
19 890
19 970
38 500
22 100
21 700
23 500
1.19
1.28
1.37
1.28
0.124
0.111
0.111
0.109
a Monomer conversion determined by 1H NMR (calculated from Eqn. 2).
b Yield determined gravimetrically.
c calculated from Eqn. 1.
d Number-average molar mass obtained from 1H NMR using conversion of monomer (calculated from Eqn. 5).
e Number-average molar mass obtained from TD-SEC.
f ĐM = Mw/Mn obtained from TD-SEC.
g obtained from TD-SEC
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8 A. A. Al-Juhni and B.-m. Z. Newby, Prog. Org. Coat., 2006, 56
,
135.
4. Conclusion
9 E. Almeida, T. C. Diamantino and O. de Sousa, Prog. Org.
Coat., 2007, 59, 2.
10 M. S. Acevedo, C. Puentes, K. Carreño, J. G. León, M.
Stupak, M. García, M. Pérez and G. Blustein, Int. Biodeterior.
Biodegradation, 2013, 83, 97.
11 M. Pérez, M. García, M. Sánchez, M. Stupak, M. Mazzuca, J.
A. Palermo and G. Blustein, Int. Biodeterior. Biodegradation,
2014, 89, 37.
12 C. L. Alzieu, J. Sanjuan, J. P. Deltreil and M. Borel, Mar. Poll.
Bull., 1986, 17, 494.
13 C. Alzieu, J. Sanjuan, P. Michel, M. Borel and J. P. Dreno,
Mar. Poll. Bull., 1989, 20, 22.
14 D. V. Ellis and L. Agan Pattisina, Mar. Poll. Bull., 1990, 21
248.
15 M. M. Saavedra Alvarez and D. V. Ellis, Mar. Poll. Bull.,
1990, 21, 244.
16 T. Nakanishi, J. Toxicol. Sci, 2008, 33, 269.
17 H. K. Okoro, O. S. Fatoki, F. A. Adekola, B. J. Ximba and R. G.
Snyman, Asian J. Chem., 2011, 23, 473.
18 Y. Kotake, Biol. Pharm. Bull., 2012, 35, 1876.
19 R. A. Braithwaite and R. L. Fletcher, J. Exp. Mar. Biol. Ecol.,
2005, 322, 111.
20 F. Cima, M. Bragadin and L. Ballarin, Aquat. Toxicol., 2008,
86, 299.
21 F. Gallucci, I. B. de Castro, F. C. Perina, D. M. de Souza
Abessa and A. de Paula Teixeira, Ecol. Indic., 2015, 58, 21.
22 F. Cima and L. Ballarin, Comp. Biochem. Physiol. C Toxicol.
Pharmacol., 2015, 169, 16.
In this paper, new bromotyramine-based acryloyl-triazole
monomers were synthesized with various lengths of
methylene linkers between the triazole and the aromatic
groups. Four monomers have been successfully prepared in
high yields by taking advantage of the recently developed
copper-catalyzed 1,3-dipolar cycloaddition reaction. The RAFT
process enabled access to bromotyramine-containing
homopolymers with narrow molar mass distributions and high
conversions. The length of the linker and the bromination of
the aromatic ring were shown to affect the kinetics of the
RAFT polymerization. In addition, DSC analyses demonstrated
that Tg values of homopolymers decreased with increasing the
length of the linker. The bromine atom linked to the aromatic
ring was shown to sterically affect the mobility of the polymer
backbone leading to an increase of the Tg. No significant effect
of the length of the linker on the thermal stability was
demonstrated. Further investigations will be pursued to
demonstrate that the RAFT polymerization is an effective way
to prepare bromotyramine-based diblock copolymers. In
addition, the marine bacterial anti-adhesion activity of
bromotyramine-based polymers will be investigated.
Triazolium-containing polymers could be also suitable as
matrixes to promote the antibiofouling properties of coatings.
Polytriazoliums prepared by a quaternization of the triazole
groups will be a subsequent alternative to these materials.
,
23 E. Ytreberg, J. Karlsson and B. Eklund, Sci. Total Environ.,
2010, 408, 2459.
24 E.-R. Kenawy, S. D. Worley and R. Broughton,
Acknowledgements
This work was financially supported by the Université de
Toulon (S. A. PhD grant).
Biomacromolecules, 2007,
25 B. Dizman, M. O. Elasri and L. J. Mathias,
Biomacromolecules, 2005, , 514.
8, 1359.
6
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