Submitted to Macromolecules

Tailor-made Poly(methyl Acrylate) bearing Amantadine

Fo
Functionality (Amino Adamantyl) via Atom Transfer Radical
Polymerization (ATRP); A Precursor of Supramolecular
Crosslinked Polymer
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Journal: Macromolecules

Manuscript ID: ma-2009-00225g.R1

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Manuscript Type: Article

Date Submitted by the

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Author:

Complete List of Authors: Singha, Nikhil; Indian Institute of technology, Rubber Technology
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Centre
Kavitha, Amalin; Indian Institute of technology, Rubber Technology
Centre
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Page 1 of 39 Submitted to Macromolecules

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5 Tailor-made Poly(methyl Acrylate) bearing Amantadine Functionality
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(Amino Adamantyl) via Atom Transfer Radical Polymerization
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(ATRP); A Precursor of Supramolecular Crosslinked Polymer
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15 A. Amalin Kavitha, Nikhil K. Singha*
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Rubber Technology Centre, Indian Institute of Technology, Kharagpur, India 721302
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Correspondence at this address; Indian Institute of Technology, Rubber Technology
51 Centre, Kharagpur 721302, India; Tel.: +91 3222 283178. Fax.: +91 3222 255303.
52 E-mail: nks@rtc.iitkgp.ernet.in
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ABSTRACT:
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5 Poly(methyl acrylate)s bearing amino adamantyl group were prepared via atom
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transfer radical polymerization (ATRP). Amino adamantyl (amantadine) group was
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10 incorporated into the polymer by homopolymerization as well as by copolymerization of
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12 acrylate bearing amantadine functional group. The rate of ATRP was slow compared to
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15 the rate of ATRP of methyl acrylate or adamantyl containing acrylate. It is due to the
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17 interaction of amine group of amantadine with Cu catalyst. 1HNMR, matrix assisted laser
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19 desorption ionisation time-of-flight mass spectrometry (MALDI-TOF-MS) and gel
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22 permeation chromatography (GPC) analysis showed that the polymers had well-defined
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24 molecular weight and amino adamantyl functional group. Interestingly, this amine group
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was further reacted with epoxy group of the tailor-made poly(glycidyl methacrylate)
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29 (PGMA) to produce hydrogen bonded polymers having porous network structure. It was
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evidenced by field-emission scanning electron microscopy (FESEM) analysis,
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differential scanning calorimetry (DSC) analysis as well as by molecular modeling.
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38 Keywords: Amantadine, ATRP, Hydrogen bonding
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Introduction
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5 Since its discovery in 1995, atom transfer radical polymerization (ATRP) has
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rapidly attracted growing interest of polymer chemists, because of its versatility in the
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10 synthesis of polymers with predictable molecular weights, low polydispersities, and
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12 specific functionalities.1,2 In ATRP, monomers as well as initiators containing functional
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15 groups are most often used in order to synthesize functional polymers.1-4 Anto et al5
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17 reported that the functional groups interfere with the ATRP catalytic system. It is
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19 therefore often necessary to use the functional groups in a protected form.5-7 Chaumont et.
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21 8
22 al reported the end functionalization of bromo-terminated polystyrene with
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24 tetraphenylethane-based derivatives by living free radical polymerization. Matyjaszewski
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et al reported carboxylic acid terminated polystyrene by ATRP. This kind of end
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29 functionalized polymers can be used to prepare polymer with well-defined architectures,
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such as various block copolymers, as well as grafted and hyperbranched materials. The
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acrylic-based polymers have interesting optical and mechanical properties. They are
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36 bioinert or biocompatible, and are therefore finding important applications in industrial
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38 uses as well as in the biomedical field.9 The amine functional group is one of the most
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fundamental motifs found in chemistry and biology, and it has been studied extensively
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43 in the past century.10 Amino and carboxylate substituted adamantane derivatives have
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45 proven to be valuable tools in both physical organic and medicinal chemistry.11 Amine
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48 groups are also used to react with epoxy-containing polymers.
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50 This investigation reports the incorporation of amino adamantyl (amantadine)
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functional groups into the poly(methyl acrylate)s by using ATRP. Structurally,
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55 amantadine (C10H15NH2) is an amino derivative of the parent molecule adamantane
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57 (C10H16), a cage-like hydrocarbon that has pharmaceutical significance.12 It is commonly
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available under the trade names of Symadine and Symmetrel. It is mainly used as anti-
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6 viral13 and anti-Parkinsonian14 drugs and has been established very effective in the
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8 prophylaxis and treatment of influenza A virus infections.15-19 Polymers containing
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specialty functional groups can be used for the treatment of various diseases.20, 21
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13 Adamantane, the parent molecule of amantadine is highly thermally stable.22 Radical
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15 polymerization using adamantyl containing monomer or initiator leads to faster
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18 polymerization rate.22, 23
Polymers containing adamantyl group have high thermal
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20 stability as well as higher glass transition temperature (Tg). The incorporation of the
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22 amantadine into the polymers can have potential applications such as high temperature
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25 resistant material and materials for biomedical applications.
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27 The present study reports the synthesis of methyl acrylate (MA) bearing
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amantadine via protection-deprotection synthon and the first example of ATRP of this
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32 specialty monomer. The polymers were characterized by 1HNMR, MALDI-TOF and
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GPC analysis. Interestingly, the active –NH2 group was reacted with the epoxy group in
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the polyglycidyl methacrylate (PGMA) leading to hydrogen bonded porous network, as
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39 evidenced by SEM, FT-IR and DSC analysis.
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41 Experimental section:
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43 Materials: 3-Amino-1-adamantanol (96 %), 2-bromoisobutyryl bromide (98 %), di-tert-
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butyl dicarbonate (99%), 1-adamantane methanol (99 %, Aldrich) and Trifluoroacetic
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48 acid (TFA) (99 %, Aldrich) were purchased from Aldrich chemicals USA, and were used
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50 as received. The monomers, glycidyl methacrylate (GMA) (97 %, Aldrich), methyl
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methacrylate (MMA) (99 %, Aldrich) and methyl acrylate (MA) (99 %, Aldrich) were
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55 purified by vacuum distillation prior to use. Acryloyl chloride (96%, Fluka) was distilled
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57 and the fraction boiling between 74°C and 79°C was collected and stored in refrigerator
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prior to use. AdMA was synthesized from 1-adamantane methanol and acryloyl chloride
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6 following standard procedures.24 Triethylamine (TEA, S.D. Fine chemicals, Mumbai,
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8 India) was dried over KOH and distilled before use. Dichloromethane (DCM, S.D. Fine
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chemicals, Mumbai, India), was dried over anhydrous CaCl2 and was distilled over
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13 anhydrous P2O5 before use. Tetrahydrofuran (THF, S.D. Fine chemicals, Mumbai, India)
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15 was refluxed over sodium and distilled twice before use. Toluene (S.D. Fine chemicals,
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18 Mumbai, India) was purified by vacuum distillation over CaH2. Azobisisobutyronitrile
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20 (AIBN, ACROS Chemical, 98 %) was recrystallized from methanol. CuBr (Aldrich,
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22 USA) was purified by washing with glacial acetic acid, followed by diethyl ether, and
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25 then dried under vacuum. Methyl 2-bromopropionate (MBrP) (97%), ethyl 2-
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27 bromoisobutyrate (EBiB) (98%), 4,4’-di (5-nonyl)-2,2’-bipyridine (dNbpy) (97%), N, N,

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N′, N″, N″ pentamethyl diethylenetriamine (PMDETA) were obtained from Aldrich,
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32 USA and were used as received.
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34 Synthesis:
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36 The monomer bearing amino adamantyl group was synthesized according to Scheme 1.
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38 Synthesis of monomer, 3-amino adamantyl acrylate (Am-AdA) (III):
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40 Synthesis of compound (I): A solution of di-tert-butyl dicarbonate (3.64 g, 1.67
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42 x 10-2 mol) in 10 ml of dry THF was slowly added into a stirred solution of 3-amino
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44 adamantanol (4.00 g, 2.39 x 10-2 mol) in 10 ml of dry THF was taken in a 100 ml three-
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47 necked round-bottom flask under cooled in a ice bath condition. Triethyl amine (TEA)
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49 (1.20 g, 1.19 x 10-2 mol) was added into the round-bottomed flask under nitrogen
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atmosphere. And the stirring was continued for 5 h. Then the reaction mixture was stirred
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54 at room temperature for 12 h. After the removal of THF, 20 ml of ethyl acetate was added
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56 to the reaction mixture. The organic layer was washed with distilled water, later with
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brine solution and was finally dried over anhydrous Na2SO4. The organic layer was
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6 filtered and concentrated. The final product was recrystallized from methanol and the
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8 resultant product was pale yellowish solid. Yield = 4.52 g (80%). 1HNMR, δ = 1.37 (s,
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9H, C9, CH3), 1.55 (s, 6H, C(2)H2), 1.61-1.76 (m, 6H, C(4) H2), 2.13 (s, 2H, C(5) –CH-),
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13 4.72 (-OH) and 5.76 (-NH-CO-) ppm; 13CNMR, δ = 70.21 (C1, ≥C-OH), 35.78 (C2), 67.9
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15 (C3, ≥C-NH-), 40.25 (C4), 31.53 (C5), 175.01 (C7, -NH-C=O-), 80.65 (C8, -OC≤) and
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18 33.25 (C9) ppm.
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20 OH
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2 2 CH3
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24 5 24 3 9
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O CH3
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33 Synthesis of compound (II): Compound I (4.00 g, 1.49 x 10-2 mol) was
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35 dissolved in 10 ml of dry THF and dry triethyl amine (1.20 g, 1.18 x 10-2 mol) were taken
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38 in a 100 ml of three necked round-bottom flask, and the contents were cooled with ice
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40 and acryloyl chloride (2.72 g, 3.02 x 10-2 mol) was added dropwise under nitrogen
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atmosphere for 5 h. The reaction mixture was brought to room temperature and was left
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45 stirring for another 12 h. The reaction mixture was then poured into water and extracted
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47 with dichloromethane. The organic layer was washed with water and brine solution and
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50 was finally dried over anhydrous Na2SO4. The organic layer was filtered and the pure
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52 product was obtained as a viscous liquid via vacuum distillation. Yield = 4.97 g (75%).
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54 HNMR, δ = 1.37 (s, 9H, C9, CH3), 1.54 (s, 6H, C(2)H2), 1.60-1.76 (m, 6H, C(4) H2),
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57 2.10 (s, 2H, C(5) –CH-), 5.76 (-NH-CO-), 5.19 and 5.70 (s, 3H, CH2=CH- (C12 and C11),
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ppm; CNMR, δ = 81.37 (C1), 35.77 (C2), 67.6 (C3, ≥C-NH-), 40.23 (C4), 31.53 (C5),
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6 175.11 (C7, -NH-C=O-), 80.66 (C8, -OC≤), 33.23 (C9 –CH3), 170.02 (C10, C=O), 130.46
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26 II
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Synthesis of compound (III): Compound II (4.50 g, 1.40 x 10-2 mol) was dissolved in 3
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ml of dry dichloromethane were placed in a three-neck round bottom flask. A mixture of
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33 trifluoroacetic acid and dry dichloromethane mixture (TFA: DCM) at 1:1 equivalence
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was added slowly to the round-bottom flask under stirring at room temperature. The final
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38 products were poured into distilled water and were extracted with dichloromethane. The
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40 extract was washed with water, brine solution and dried over anhydrous sodium sulfate,
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43 the organic layer was filtered and passed through the column and concentrated. The final
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45 product was yellowish viscous liquid yielding at 3.23 g (72%). 1HNMR, δ = 1.56 (s, 6H,
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47 C(2)H2), 1.61-1.76 (m, 6H, C(4) H2), 2.12 (s, 2H, C(5) –CH-), 3.74 (-NH2, C6), 5.20 and
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50 5.71 (3H, CH2=CH-, (C9 and C8)) ppm; 13CNMR, δ = 81.32 (C1), 35.75 (C2), 66.8 (C3,
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CH2 =) ppm.
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4 NH2
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21 Atom Transfer Radical Polymeriaztion (ATRP):
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23 Homopolymerization of 3-amino adamantyl acrylate (Am-AdA) (III): In a

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typical polymerization procedure, CuBr (0.025 g, 1.80 x 10-4 mol) and the ligand, dNbpy
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28 (0.073 g, 1.80 x 10-4 mol) were placed in a 50 ml three neck round bottom flask. The
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30 monomer, Am-AdA (III) (2.00 g, 9.04 x 10-3 mol) was then added. The flask was
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33 equipped with a condenser in one neck and a silicone rubber septum in the other. The
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35 polymerization was carried out under nitrogen atmosphere. The polymerization was
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40 out at 700C. At different time intervals, the sample was withdrawn under nitrogen
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42 atmosphere and a part of it was used for the gravimetric determination for monomer
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conversion. The remaining sample was passed through an alumina column to remove the
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47 catalyst and then was dried under vacuum at 45° C. Yield: 0.99 g (50 %). Mn(GPC) =
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49 5572, (Mn(theo) = 5611) and Mw/Mn = 1.33. 1HNMR, δ = 1.38 and 2.28 (>CH2 and >CH-
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of main chain back bone), 1.57 (s, 6H, >CH2, (b1)), 1.63-1.79 (m, 6H, >CH2, (b3)), 2.01 (s,
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54 2H, >CH-, (b2)), 3.74 (-NH2) and 3.65 (>CH-Br, chain end group of the polymer) ppm.
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Copolymerization of Am-AdA (III) and methyl acrylate (MA): In this case,
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6 the copolymerization of Am-AdA and MA was carried out at a feed ratio of 40:60
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8 respectively. In a typical polymerization procedure, CuBr (0.032 g, 2.26 x 10-4 mol) and
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dNbpy (0.092 g, 2.26 x 10-4 mol), were taken in a three neck round bottom flask. The
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13 monomers, Am-AdA (III) (2.00 g, 9.04 x 10-3 mol) and MA (1.16 g, 1.35 x 10-2 mol)
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15 were added into the flask under nitrogen atmosphere. The flask was equipped with a
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18 condenser in one neck and a silicone rubber septum in the other. Then the flask was
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placed into the oil bath already heated 700C. The copolymerization was started by adding
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22 methyl 2-bromo propionate (0.037 g, 2.26 x 10-4 mol) into the flask. At different time
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25 intervals, the sample was taken out under nitrogen atmosphere. The copolymer
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through an alumina column to remove the catalyst and then dried under vacuum at 45° C.
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32 Yield: 1.42 g (45 %). Mn(GPC) = 6300, (Mn(theo) = 6425) and Mw/Mn = 1.38. 1HNMR, δ
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= 1.37 and 2.29 (>CH2 and >CH- of main chain back bone), 1.57 (s, 6H, >CH2 of
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adamantyl protons, (b1)), 1.63-1.79 (m, 6H, >CH2 of adamantyl protons, (b3)), 2.01 (s,
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39 2H, >CH- of adamantyl protons, (b2)), 3.55 (3H, –OCH3 of MA protons), 3.74 (-NH2)
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41 ppm. The copolymer composition determined by 1HNMR was 25% of PAm-AdA and
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44 75% of PMA.
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46 Synthesis of the Diblock Copolymer (PAm-AdA-b-PMMA): The diblock
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copolymer was synthesized by the chain extension experiment of PAm-AdA using as a

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51 macroinitiator (0.50 g, 8.97 x 10-5 mol, Mn(GPC) = 5572, Mw/Mn = 1.33) by the addition
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of fresh MMA (0.89 g, 8.97 x 10-3 mol) as the monomer. Synthesis of the diblock
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copolymer was carried out on the similar method as described for the
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homopolymerization of Am-AdA. The different chemicals were used, CuBr (0.012 g,
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6 8.97 x 10-5 mol) as catalyst, PMDETA (0.015 g, 8.97 x 10-5 mol) as ligand and PAm-AdA
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8 (0.50 g, 8.97 x 10-5 mol) as macroinitiator instead of methyl 2-bromo propionate. Yield:
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0.79 g (57 %). Mn(GPC) = 8817, (Mn(theo) = 8876) and Mw/Mn = 1.35. 1HNMR, δ =
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13 0.81–1.04 (3H, -CH3 of PMMA), 1.20–2.10 (2H, >CH2 protons of PMMA unit and 14H
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15 of >CH2, >CH- of the PAm-AdA (adamantyl group) initiator part), 3.50 (3H, -OCH3 of
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18 PMMA), 3.74 (2H, -NH2 of PAm-AdA initiator part) ppm.
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20 Preparation of polyglycidyl methacrylate (PGMA): PGMA was prepared by
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22 using GMA:CuBr:PMDETA:EBiB at the ratio of 50:1:1:1 at room temperature via ATRP
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25 method. The same procedure was adopted as for the ATRP of Am-AdA (III) as described
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27 earlier. Yield: 1.81 g (91 %). Mn(GPC) = 5865, (Mn(theo) = 5911) and Mw/Mn = 1.21.
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29 1
HNMR, δ = 0.92 to 2.16 (5H, -CH3 and >CH2 of main chain back bone), 2.62 and 2.83
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32 (2H, >CH2 of epoxy group), 3.23 (1H, >CH- of epoxy group), 3.79 and 4.30 (2H, -OCH2)
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ppm.
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One-pot synthesis of hydrogen bonded polymer (VI)
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39 Poly (glycidyl methacrylate) (PGMA) (1.00 g, 1.70 x 10-4 mol) (Mn = 5865,
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41 Mw/Mn = 1.21) and PAm-AdA (VI) (0.95 g, 1.70 x 10-4 mol) (Mn = 5572 and Mw/Mn =
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44 1.33) were dissolved in a 25 ml of dry toluene in a 100 ml round-bottom flask under
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46 nitrogen atmosphere. The mixture was refluxed at 120 °C for 9 h under constant stirring.
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Then the reaction mixture was allowed to cool at room temperature. The pale yellowish
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51 white colored solid material was precipitated itself during the reaction. The resultant
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Instrumentation:
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5 The GPC measurement was performed at ambient temperature using a Viscotek
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GPC equipped with a refractive index detector (model VE 3580). The polymer solution
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10 was passed through two ViscoGEL GPC columns (model GMHHR-M #17392)
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12 connected in series. The GPC columns were mixed bed columns having pore size of 30-
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15 650 Å and were suitable for the polymer of medium to high molecular weights (exclusion
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17 limit Mn = 1 x 106). THF was used as eluent at room temperature with a flow rate of 1.0
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19 ml/min. Linear PMMA standards (Polymer Laboratories) were used as calibration
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22 standard. Data acquisition and processing were performed using Viscotek OMNI-01
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24 software. 1H (400 MHz) and 13C (125 MHz) NMR spectra were recorded on a Bruker 400
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spectrometer using CDCl3 as solvent which had a small amount of TMS as internal
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29 standard. Infrared spectra were recorded on a Perkin-Elmer, Inc. version 5.0.1
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31 spectrophotometer. In this case a dilute solution of the polymer sample in chloroform was
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film cast over KBr cells and then the IR spectra were recorded. FTIR spectra were
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36 recorded in the range of 4000–400 cm-1. Mass spectra were acquired on a Perceptive
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38 Biosystems Voyager Elite MALDI-TOF mass spectrometer, equipped with a nitrogen
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laser (wave length 337 nm). Polymer samples, 2,5-dihydroxybenzoic acid (used as
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43 matrix) and sodium trifluoroacetate (used as a cationic agent) were dissolved in THF (10
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mg/ml solutions of each component) and the resulting solutions were mixed at 100/100/1
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48 volume ratio. All the spectra were averaged over 128 laser shots. Differential Scanning
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50 Calorimetry (DSC) analysis was carried out using a “Pyris Diamond DSC, Perkin Elmer,
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(UK)" under nitrogen atmosphere at a heating rate of 20 °C/min. The glass transition
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55 temperature (Tg) was calculated from the inflexion point in the second heating cycle. The
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57 baseline was calibrated by scanning the temperature domain of the experiments with an
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empty pan. The enthalpy was calibrated with an indium standard, as well as the heat
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6 capacity was calibrated by measuring with sapphire disc supplied by Perkin Elmer
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8 Instruments. The temperature calibration was performed with different metal standards at
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the various heating rates. UV-vis spectroscopic measurements were performed at 25 °C
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13 on a Hewlett-Packard diode array UV-vis spectrometer, using a quartz UV cell. UV and
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15 visible electronic spectra were recorded at a concentration of 5.0 x 10-4 mol/L in
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18 tetrahydrofuran in λ = 190–1000 nm. The morphological study of the polymers was
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20 performed using an SEM model JSM800 manufactured by JEOL at 20 kV acceleration
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22 voltage at room temperature. The pore size of the polymer was measured using image
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24
25 processing software, "Image tool version 3.0". The modeling study for hydrogen bonded
26
Co

27 polymer was performed with ‘DMol3’ molecular modeling software. The optimization of
28
29
the hydrogen bonded structure was made using Gaussian 03 Package.
30
nf

31
32 Results and Discussion
33
The synthesis of 3-amino adamantyl acrylate (III), an amino adamantyl
id

34
35
36 (amantadine) containing monomer was carried out by a three-step synthetic procedure
en

37
38 (Scheme 1). In this case the first step is the reaction between 3-amino adamantanol and
39
40
di-tert-butyl dicarbonate to generate amine protected 3-amino adamantanol (I). In the
tia

41
42
43 second step this amine protected compound was reacted with acryloyl chloride to obtain
44
l-

45
the structure II (in Scheme 1), the amine protected monomer. The final step is the
46
47
48 cleavage of di-tert-butyl dicarbonate by the addition of 1:1 mixture of trifluoro acetic
AC

49
50 acid/dichloromethane to obtain the resultant monomer, 3-amino adamantyl acrylate (III)
51
52
(Am-AdA). The Am-AdA was polymerized using CuBr/dNbpy as catalyst and methyl
S

53
54
55 bromo propionate as initiator (Scheme 2). The plot of ln(1/1-x) vs reaction time shows
56
57 linear indicating the concentration of active species is constant throughout the reaction.
58
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The comparative kinetic plots of the ATRP of Am-AdA, MA and AdMA (adamantyl
4
5
6 methyl acrylate) are shown in Figure 1a. The rate of polymerization of Am-AdA is
7
Fo
8 slower than that of MA and AdMA. Figure 1b shows that there is gradual increase in
9
10
11
molecular weight (Mn) with conversion maintaining relatively low polydispersity index
rR
12
13 (PDI = Mw/Mn). The conversions as well as the molecular weights of the polymers at
14
15 different time interval are much less in the ATRP of Am-AdA than that in the ATRP of
16
ev
17
18 AdMA (Figure 1a and 1b). The polydispersity index of the PAm-AdA is relatively
19
ie
20 broader than PAdMA or PMA. It is due to the probable coordination between copper
21
22 catalyst and amine group in the monomer which slows the dynamics of the equilibrium
w.

23
24
25 between the dormant species and active species. Controlled experiments were carried out
26
Co

27 to elucidate the nature of interaction between copper catalyst and –NH2. Figure 2
28
29
indicates that the solution of CuBr and Am-AdA is homogeneous (Figure 2a) whereas the
30
nf

31
32 solution of CuBr in AdMA or in MA is heterogeneous (figure 2b and Figure 2c).
33
Figure 3 shows the UV-vis spectra of the Am-AdA and the mixture of Am-AdA
id

34
35
36
and CuBr in THF. The solution of Am-AdA in THF shows a characteristic absorption
en

37
38
39 peak at 334 nm while Am-AdA/CuBr shows at 310 nm wavelength (Figure 3a). After the
40
tia

41 addition of CuBr into Am-AdA solution, the color gradually changed from light yellow to
42
43
44 green at room temperature, and the intensity of the characteristic absorption peak
l-

45
46 decreased over 10 h (Figure 3b). The decrease in the intensity of the absorption peak at
47
48
AC

310 nm is due to the interaction between NH2 moieties and Cu ions. It is reported that
49
50
51 aliphatic tertiary amines can interact with copper ions.25-28 Figure 2 shows that CuBr is
52
S

53 soluble in Am-AdA, but insoluble in AdMA or MA. It indicates that –NH2 group in Am-
54
55 28
56
AdA form complex with CuBr. Haddletone et al reported that the reactivity of
57
58
59
60
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aminoethyl methacrylate differs significantly due to a strong coordination between the
4
5
6 monomer and copper catalyst in ATRP. Baskaran et al29 reported the ATRP of methyl
7
Fo
8 vinyl ketone (MVK) using CuBr as catalyst. They failed to prepare homopolymer of
9
10
11
MVK, because the carbonyl chromophore of MVK was participating in complexation
rR
12
13 with Cu catalyst. In the present case the coordination between –NH2 group in the
14
15 monomer and copper catalyst decreases the rate of ATRP. In a controlled experiment,
16
ev
17
18 conventional radical polymerization of Am-AdA using azobisisobutyronitrile (AIBN) led
19
ie
20 to very high conversion (89% conversion at 3 h, Mn = 18760, Mw/Mn = 2.1) during
21
22 polymerization, whereas ATRP of Am-AdA shows conversion 50% in 10 h. It also
w.

23
24
25 indicates that the interaction of –NH2 in Am-AdA with ATRP catalyst affects the
26
Co

27 polymerization reaction.
28
29
Figure 4a shows the 1HNMR spectra of the homopolymer of Am-AdA. The
30
nf

31
32 resonance at δ = 3.74 ppm is due to the proton of ‘-NH2’ group of the adamantyl group
33
(designated as ‘a’ in Figure 4a). The resonances at 1.38 and 2.28 ppm are due to the
id

34
35
36
methylene (–CH2-) and methine (>CH-) protons in the main chain back bone of the
en

37
38
39 polymer (as designated at ‘c and d’ respectively). The resonances at 1.57 and 1.63-1.79
40
tia

41 ppm are due to the two different types of >CH2 protons in the adamantyl group (as
42
43
44 designated at ‘b1’ and ‘b3’ respectively, Figure 4a). The resonances at 2.01 ppm is due to
l-

45
46 the >CH- (designated as ‘b2’ in Figure 4a) proton in the adamantyl group. The small
47
48
AC

resonance at 3.65 ppm is attributed to the proton of >CH-Br (chain end group of the
49
50
51 polymer).
52
S

53 The copolymerization of Am-AdA and MA (feed ratio 40:60) was carried out
54
55
56
using the dNbpy/CuBr catalyst using methyl-2-bromo propionate as initiator (Scheme 2).
57
58
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Figure 4b shows the 1HNMR spectrum of the PAm-AdA-co-PMA (40:60). The resonance
4
5
6 at 3.55 ppm is attributed to the –OCH3 of MA protons (designated as ’e’ in Figure 4b).
7
Fo
8 The resonance at 3.74 ppm is due to the ‘-NH2’ protons (designated as ’a’ in Figure 4b)
9
10
11
of the PAm-AdA. The resonances at 1.57 [>CH2 (b1)], 1.63-1.79 [>CH2- (b3)] and 2.01
rR
12
13 [>CH- (b2)] ppm are due to the three types of adamantyl protons. The resonances at 1.37
14
15 and 2.29 ppm are due to the different aliphatic protons (–CH2- and >CH-) of the PAm-
16
ev
17
18 AdA and PMA protons in the main chain back bone as designated as ‘c and d’
19
ie
20 respectively. The copolymer composition was calculated from the integration ratio of the
21
22 peak intensities of the protons –NH2 (δ = 3.74 ppm designated as ‘a’ in Figure 4b) and –
w.

23
24
25 OCH3 of (δ = 3.55 ppm designated as ‘e’ in Figure 4b) PAm-AdA and PMA units
26
Co

27 respectively. The final copolymer (PAm-AdA-co-PMA) composition was 25% of PAm-

28
29
AdA and 75% of PMA. The less incorporation of PAm-AdA clearly indicates the slow
30
nf

31
32 reactivity or the slow rate of polymerization. In a controlled experiment, when
33
conventional radical copolymerization of Am-AdA and MA (feed ratio 40:60) was
id

34
35
36
carried out using AIBN as initiator, there was 76 % conversion at 5 h. The final
en

37
38
39 copolymer (PAm-AdA-co-PMA) composition was 56 % of PAm-AdA and 44 % of
40
tia

41 PMA. It clearly indicates that the complexation of copper catalyst with the monomer
42
43
44 affects the rate of ATRP as well as its incorporation into the copolymer. It is reported that
l-

45
46 in the radical copolymerization (in conventional22 as well as in ATRP24) using acrylates
47
48
AC

containing adamantyl group, the incorporation of this monomer is much higher than the
49
50
51 other comonomer. In this case less incorporation of the PAm-AdA compared to that of
52
S

53 PMA is attributed to complex formation between monomer (PAm-AdA) and catalyst

54
55
56
(CuBr) which alters the reactivity of the monomers.
57
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The presence of amino-adamantyl group in the polymers was confirmed by
4
5
6 MALDI-TOF MS analysis (Figure 5). In the MALDI experiments, sodium trifluoroacetic
7
Fo
8 acid was used as the cationic agent. All macromolecular chains have sodium ion as the
9
10
11
cationic agent, and they were detected at m/z value 23 Da above the theoretically
rR
12
13 calculated values. The mass series (M) appearing in the MALDI TOF-MS spectra can be
14
15 expressed as follows:
16
ev
17
18 M = M1 + nMr + Mendgroup + Mcation (1)
19 Where, M1, Mr, Mendgroup and Mcation are the masses of the initiator moiety (methyl-2-
ie
20
21
22 bromo propionate [MBrP] = 87), monomer (Am-AdA = 221), repeat unit (n), end groups
w.

23
24 (-Br = 80) and cation (Na = 23) respectively, and n stands for the degree of
25
26
polymerization. The isotopic distribution of each peak was compared with those peaks
Co

27
28
29 simulated with Isopro-3 and then the peaks were assigned carefully. Figure 5b shows the
30
nf

31 expand MALDI spectrum of the PAm-AdA. The difference in molecular weight of each
32
33
intense peak is 221 which is the molecular weight of 3-amino adamantyl acrylate (Am-
id

34
35
36 AdA). The peak at 2621 is attributed to the structure-a. It clearly shows that each
en

37
38 macromolecular chain has methyl propionate [-CH(CH3)CO2CH3] and –Br end groups.
39
40
The average molecular weight and polydispersity index (Mw/Mn) of PAm-AdA
tia

41
42
43 determined by MALDI was 5652 (Mn) and 1.33 (Mw/Mn) respectively (Mn,GPC = 5572
44
l-

45
and Mw/Mn = 1.33). The –Br end group was further confirmed by the chain extension
46
47
48 experiment of the polymer PAm-AdA as macroinitiator and by the addition of fresh
AC

49
50 MMA. Formation of the diblock copolymer was confirmed by 1HNMR and GPC
51
52
analysis. There was shift of GPC traces towards higher MW in GPC chromatogram
S

53
54
55 (Figure 6). In the 1HNMR spectrum there was an emergence of a new peak at δ = 3.5
56
57 ppm which is due to the proton of –OCH3 group of MMA part.
58
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Reaction between poly(amino-adamantyl acrylate) (PAm-AdA) and polyglycidyl
4
5 methacrylate (PGMA): A supramolecular Polymer.
6
7 The hydrogen bond is a unique phenomenon in structural chemistry and biology.30
Fo
8
9 In supramolecular chemistry the hydrogen bond is able to control and direct structures of
10
11
molecular assemblies, because it is sufficiently strong and sufficiently directional.31 The
rR
12
13
14 polyacrylates bearing amantadine polymers can have interesting applications because of
15
16
ev
the presence of the hydrogen-bonding motifs (-NH2) for the design of supramolecular
17
18
19 architectures. The presence of -NH2 group in the polymers prepared so far was further
ie
20
21 confirmed by the thermal crosslinking reaction between amine and epoxy group. This
22
w.

23
24
kind of reaction is used in many applications such as in adhesives, in protective coatings,
25
26 in microelectronics, and in different composite applications. 32-35 The epoxy-amine is also
Co

27
28 used to prepare porous thermosetting materials which can be used as selective permeation
29
30
membranes32 and as substrates for nanocomposite fabrication.33 In this investigation we
nf

31
32
33 carried out the reaction between poly (amino adamantyl acrylate) [prepared by ATRP,
id

34
35 Mn = 5572 and Mw/Mn = 1.33] and poly (glycidyl methacrylate) [prepared by ATRP,
36
en

37
38 Mn = 5865 and Mw/Mn = 1.21] having epoxy pendant group. Scheme 3 shows the
39
40 reaction between the amine group and the epoxy group in the tailor-made polymers
tia

41
42
43
which leads to the formation of –NH- and –OH groups and subsequently the
44
l-

45 intermolecular hydrogen bonding.

46
47 The reaction between amine and epoxy group was investigated by FTIR
48
AC

49
50 spectroscopy as shown in Figure 7. The PGMA (Figure 7a) shows the epoxy band at 910
51
52 cm-1 and the carbonyl band at 1722 cm-1. The PAm-AdA (Figure 7b) shows the broad
S

53
54 bands at 3320 cm-1 due to the primary amine (-NH2) and the peak at 1721 cm-1 due to the
55
56
57 carbonyl group (CO). Figure 7c shows the reaction between PAm-AdA and PGMA. In
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this case a new strong band appears at 3382 cm-1 due to the formation of hydroxyl groups
4
5
6 (-OH) by the ring opening of the epoxy group in the PGMA unit. Normally the free OH
7
Fo
8 band appears at around 3600 cm-1.36 The broad absorption band positions at 3376-3387
9
10
11
cm-1 are attributed to the hydrogen bonded –OH. It indicates that the hydroxyl groups of
rR
12
13 PGMA-PAm-AdA (polymer VI) are mostly hydrogen bonded. Interestingly, there was
14
15 emergence of a new shoulder peak at 3230 cm-1 which is attributed to the formation of
16
ev
17
18 the secondary amine (-NH-). These FTIR spectra show clear evidence for the reaction of
19
ie
20 PGMA with PAm-AdA and the formation of hydrogen bonding in the polymer.
21
22 Figure 8 shows the surface topography of the hydrogen bonded polymer (VI) by
w.

23
24
25 field emission scanning electron microscopy (FESEM) analysis. Figure 8a and 8b show
26
Co

27 the FESEM images of PGMA and PAm-AdMA respectively, and figure 8c and 8d show
28
29
the FESEM images of the hydrogen bonded polymer (Polymer (VI) at different
30
nf

31
32 magnifications. It is observed that the hydrogen bonded polymer (Polymer (VI) has the
33
porous network structure (Figure 8c and 8d). Raman et al37 reported the formation of
id

34
35
36
nanoporous polymer materials during the reaction between diglycidyl ether of bisphenol
en

37
38
39 A and 4,4’ methylenebiscyclohexanamine and proved this by SEM analysis. During the
40
tia

41 step-growth polymerization reaction of epoxy-amine system, OH group in the polymer

42
43
44 interacts with the oxygen in THF to form hydrogen bonding, resulted in the final polymer
l-

45
46 structure with porous network.37-38 In our case the porous network structure is due to the
47
48
AC

reaction between epoxy group (in the tailor-made PGMA) and –NH2 group (in PAm-
49
50
51 AdA) and due to the hydrogen bonding between the –OH group and –NH- generated in
52
S

53 situ thereof (Scheme 3). The pore size was calculated to be 0.62 µm using image
54
55
56
processing software, "Image tool version 3.0".
57
58
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60
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The evidence of hydrogen bonding interaction of polymer (VI) was confirmed by
4
5
6 molecular modeling using ‘DMol3’ software. The optimization of the hydrogen bonded
7
Fo
8 structure was made by using Gaussian 03 Package.39 The initial structure (the output
9
10
11
hydrogen bonded structure from ‘DMol3’) as an input file was made through Gauss
rR
12
13 View.39 The results of the Gaussian output of the hydrogen bonding atoms were
14
15 visualized with the help of Gauss View39 and the assignment of the structure were made.
16
ev
17
18 The hydrogen bond lengths of -OH and –NH- are found to be 2.074 Ao and 2.347 Ao
19
ie
20 respectively. The optimized structure of polymer (VI) is shown in figure 9. This study
21
22 clearly confirmed the formation of hydrogen bond in the polymer.
w.

23
24
25 DSC Analysis:
26
DSC analysis showed the Tg of PAm-AdA and PGMA at 131°C and 55 °C,
Co

27
28
29 respectively. The higher Tg of PAm-AdA is due to the presence of bulky adamantyl
30
nf

31 group which restricts the chain mobility. The new polymeric material (polymer (VI))
32
33
prepared by the reaction between PAm-AdA and PGMA (1:1) showed a Tg of 63 °C
id

34
35
36 (Figure 10). The steric factors that caused the higher Tg of adamantane containing
en

37
38 polymer may be lowered in the polymer VI (Scheme 4), due to the formation of a flexible
39
40
side chain (-O- linkage) (figure 10) which in turn increase the free chain mobility.40
tia

41
42
43 Herman et al 40 reported that the oxirane ring opening of PGMA forms flexible and thus it
44
l-

45
reduces the Tg. Interestingly, the DSC thermogram shows an endotherm at 103 °C,
46
47
48 which may be attributed to the breakage of H-bonds41 that cause softening to the polymer
AC

49
50 chains.
51
52
Conclusion:
S

53
54 Well defined tailor-made homo as well as copolymer of amino adamantyl acrylate
55
56
57 was successfully prepared by atom transfer radical polymerization. The presence of
58
59
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amino adamantyl (amantadine) group reduces the rate of ATRP, because of the
4
5
6 interaction of amine group of amantadine with copper catalyst. This was confirmed by
7
Fo
8 UV-vis spectroscopy studies and the controlled experiments of AdMA or MA with CuBr.
9
10
11
The end group of the polymer was confirmed by 1HNMR spectroscopy, matrix assisted
rR
12
13 laser desorption ionisation time-of-flight mass spectrometry and chain extended
14
15 experiment. This analysis showed that the polymers had well-defined molecular weight
16
ev
17
18 and amino adamantyl functional group as well as all polymer chain had a well defined
19
ie
20 end group. Interestingly, the tailor-made PAm-AdA reacted with tailor-made PGMA to
21
22 prepare porous network structure having H-bonding. It was confirmed FT-IR, field
w.

23
24
25 emission scanning electron microscopy as well as by 3D-modeling studies. Differential
26
Co

27 scanning calorimetry analysis of the crosslinked porous polymer showed an endotherm at

28
29
103 °C indicating the presence of H-bonding in the polymer. These porous hydrogen
30
nf

31
32 bonded materials may have potential applications in drug encapsulation and drug delivery
33
in biomedical applications.
id

34
35
36
Acknowledgement
en

37
38
39 The authors gratefully acknowledge Department of Science & Technology (DST), New
40
tia

41 Delhi and IIT, Kharagpur (for the sanction of ISIRD project) for the financial support.
42
43
44
l-

45
References:
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47
48 (1) (a) Bednarek, M.; Biedron, T.; Kubisa, P. Macromol. Rapid. Commun. 1999, 20, 59-
AC

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50 65. (b) Matyjaszewski, K.; Wang, J. S. Macromolecules 1995, 28, 7901-7010.
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Co

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25 Biology, Oxford university press, New York 2001 pp. 1.
26
Co

27 (31) Hoogenboom, R.; Schubert, U.S.; Chem. Soc. Rev., 2006, 35, 622–629.
28
29
(32). (a) Fang, J.; Kita, H.; Okamoto, K. J. Membr. Sci. 2001,182, 245-256. (b) Wang,
30
nf

31
32 Y.; Hirakawa, S.; Wang, H.; Tanaka, K.; Kita, H.; Okamotoa, K. J. Membr. Sci. 2002,
33
199, 13-27.
id

34
35
36
(33) Raman, V. I.; Palmese, G. R. Colloids Surf. A 2004, 241, 119-125.
en

37
38
39 (34) (a) Raman, V. I.; Palmese G. R. Macromolecules 2005, 38, 6923-6930; (b) Buist, G.
40
tia

41 J.; Barton, J. M.; Howlin, B. J.; Jones J. R.; Parker, M. J. J. Mater. Chem., 1996, 6, 911-
42
43
44 915. (c) Sauvant, V.; Halary J.L. Compos. Sci. Technol. 2002, 62, 481–486.
l-

45
46 (35) (a) Lee, K. J.; Kim, Y. W.; Koh, J. H.; Kim, J. H. J. Polym. Sci.: Part B: Polym.
47
48
AC

Phy. 2007, 45, 3181-3188. (b) Yang, J.; Huang, K.; Pu, Z.; Gong, Y.; Li, H.; Hu, C. J.
49
50
51 Mole. Structr. 2006, 789,162-168.
52
S

53 (36) Noto, D. V.; Longo, D.; Munchow, V. J. Phys. Chem. B 1999,103, 2636-2646.
54
55
56
(37) Raman, V. I.; Palmese, G. R. Langmuir 2005, 21, 1539-1546.
57
58
59
60
23
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1
2
3
(38) Mijovic, J.; Fishbain, A.; Wijayat, J. Macromolecules 1992,25, 979-985.
4
5
6 (39) Singh, D.; Srivastava, S. K.; Ojha, A. J.; Asthana, B. P.; Singh, R. K. J. Mole. Str.
7
Fo
8 Theochem 2007, 819, 88–94.
9
10
11
(40) Mark, H. F. Encyclopedia of Polymer Science and Technology, Mark, H. F.Ed.; John
rR
12
13 Wiley & Sons, 2004, vol 9, p. 768.
14
15 (41) (a) Folmer, B. J. B.; Sijbesma, R. P.; Versteegen, R. M.; Rijt, J. A. J. v.; Meijer; E.
16
ev
17
18 W. Adv. Mater. 2000, 12, 874-878. (b) Scherman, O. A.; Ligthart, G. B. W. L.; Ohkawa,
19
ie
20 H.; Sijbesma, R. P.; Meijer E. W. PNAS 2006, 103, 11850-11855.
21
22
w.

23
24
25 Legends:
26
Co

27 Schemes:
28
29 Scheme 1: Synthesis of 3-amino adamantyl acrylate (Am-AdA) (III) (Monomer).
30
nf

31 Scheme 2: Atom transfer radical polymerization for incorporating amino adamantyl

32
33 group in the polymer; (a) Homo polymerization of amino adamantyl acrylate (Am-AdA)
id

34
35 (III); (b) Copolymerization of amino adamantyl acrylate (Am-AdA) (III) and methyl
36
acrylate (MA).
en

37
38
39
40
Scheme 3: Reaction between poly (amino adamantyl acrylate) (PAm-AdA) and poly
tia

41 (glycidyl methacrylate) (PGMA) and formation of hydrogen bonding in the polymer

42
43 network.
44
l-

45
46 Figures:
47
48 Figure 1: (a) Kinetic plots of ln(1/1-X) versus reaction time t, and (b) the dependence of
AC

49
50 the number-average molecular weights (Mn) and molecular weight distributions (PDI =
51 Mw/Mn) on the monomer conversion for the atom transfer radical polymerization in bulk
52
S

53 at 90°C [M0/CuBr/dNbpy/MBrP, 50:1:1:1]. (▲) Poly (amino adamantyl acrylate) (PAm-

54
55 AdA), (●) Poly (methyl acrylate) (PMA) and (■) Poly (adamantyl methyl acrylate)
56
57 (PAdMA)
58
59
60
24
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Page 25 of 39 Submitted to Macromolecules

1
2
3
Figure 2: Solutions of CuBr in amino adamantyl acrylate (Am-AdA) (4 mg/1mL) (a),
4
5 CuBr in adamantyl methyl acrylate (AdMA) (4 mg/1mL) (b), and CuBr in methyl
6
7 acrylate (MA) (4 mg/1mL) (c).
Fo
8
9
10 Figure 3: UV-vis Spectra of (a) amino adamantyl acrylate (Am-AdA) (dotted line),
11
and mixture of Am-AdA and CuBr (solid line) (both at a concentration of 5.0 x 10-4
rR
12
13
14
mol/L in tetrahydrofuran); (b) UV-vis Spectra of the mixture of Am-AdA and CuBr at
15 different time.
16
ev
17
18 Figure 4: 1HNMR spectra of the polymers (a) Homopolymer of poly (amino adamantyl
19
ie
20 acrylate) (PAm-AdA); (b) Copolymer of poly (amino adamantyl acrylate-co-poly methyl
21
22 acrylate) (PAm-AdA-co-PMA) (25:75).
w.

23
24
25 Figure 5: Matrix assisted laser desorption ionisation time-of-flight mass spectrum of
26
poly (amino adamantyl acrylate). (5a) Whole mass spectrum, (5b) Am amplified region.
Co

27
28 Figure 6: Gel permeation chromatography traces of poly (amino adamantyl acrylate)
29
30 macroinitiator and poly (methyl methacrylate-b- poly amino adamantyl acrylate)
nf

31
32 prepared by chain extension reaction.
33
id

34
35 Figure 7: FTIR spectra for (a) Poly (glycidyl methacrylate) (PGMA), (b) Poly (amino
36
adamantyl acrylate) (PAm-AdA) and (c) PGMA-PAm-AdA (1:1) (Polymer VI).
en

37
38
39
40
Figure 8: Field-emission scanning electron micrographs of the samples: Figure (a) Poly
tia

41 (glycidyl methacrylate) (PGMA), (b) Poly (amino adamantyl acrylate) (PAm-AdA),

42
43 Figure (c) and (d) Polymer (VI) [PGMA-PAm-AdA] in low and high magnification
44
l-

45 respectively.
46
47
48 Figure 9: The optimized 3D-structure of the hydrogen bonded polymer (VI) (as shown in
AC

49
50 Scheme 3).
51
52
S

53 Figure 10: Differential Scanning Calorimetric thermogram of (a) Polymer (VI) (as
54
55 shown in Scheme 3); (b) Poly (glycidyl methacrylate) and (c) Poly (amino adamantyl
56
57 acrylate).
58
59
60
25
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1
2
3
4
5
6
7
Fo
8
9
10
11
rR
12
13
14
15
16
ev
17 OH
18 CH3 O CH3
OH
O
19 Room Temperature
ie
20 + H3C O O O CH3
Triethyl amine
21 NH2 Tetrahydrofuran
22 CH3 CH3
w.
NH-BOC
23
3-Amino adamantanol Di-tert-butyl dicarbonate I
24
(BOC anhydride)
25
26
Co

27 CH2 CH
28 CH2 CH
29 Room Temperature OOC
CH2 CH Cleavage of BOC
30 I + OOC
+ Triethyl amine
nf

31 CF3COOH / CH2Cl2 (1:1)

COCl + Tetrahydrofuran
32 RT
(Acryloyl Chloride) - HCl
33
NH-BOC
id

34
35 II NH2
36 3-amino adamantyl
en

37 acrylate (Am-AdA)
38 (III) (Monomer)
39
40
Scheme 1: Synthesis of 3-amino adamantyl acrylate (Am-AdA) (III) (Monomer).
tia

41
42
43
44
l-

45
46
47
48
AC

49
50
51
52
S

53
54
55
56
57
58
59
60
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1
2
3
4
5
6
7
Fo
8
9
10
11
rR
12
13 (a) n CH2 CH
H CH3 CH CH2 CH Br
14 n
15 OOC
OOC
16 CH3 C Br + COOCH3
ev
CuBr / dNbpy
17
18 COOCH3
19 NH2
ie
20 MBrP NH2
21 Am-AdA (III)
PAm-AdA (IV)
22
w.

23 (b)
24
25 n CH2 CH
H CH2 CH Br
26 CH3 CH CH2 CH
Co

n m
27 OOC m CH2 CH CuBr / dNbpy
28 CH3 C Br + COOCH3 OOC
COOCH3
29
+
COOCH3
30 COOCH3
nf

31 Methyl Acrylate (MA)

NH2
32 NH2
33 MBrP Am-AdA (III)
PAm-AdMA-co-PMA (V)
id

34
35
36
en

37
38 Scheme 2: Atom transfer radical polymerization for incorporating amino adamantyl
39
40 group in the polymer; (a) Homo polymerization of amino adamantyl acrylate (Am-AdA)
tia

41
42 (III); (b) Copolymerization of amino adamantyl acrylate (Am-AdA) (III) and methyl
43
44 acrylate (MA).
l-

45
46
47
48
AC

49
50
51
52
S

53
54
55
56
57
58
59
60
27
ACS Paragon Plus Environment
 Submitted to Macromolecules Page 28 of 39

1
2
3
4
5
6
7
Fo
8
9
10
11
rR
12
13
14
15
16
ev
17 CH3 CH2 CH
18 CH2 CH
n
CH3
19 n CH2 C OOC
ie
n
20 OOC C
COO CH2
21 + 1200C n
22
w.
9h CH2 CH2 C
23 CH2 O
N CH
24 O
NH2 CH
25 H O
O
26
2.074 A°
Co

PAm-AdA CH2
27 H
OH
28 O 2.347 A°
29 PGMA
O NH
C CH2 CH
30 CH2
nf

31
32 CH2 C
n
33
CH3
id

34 COO
35
36 CH2 CH
en

37 n

38 Polymer (VI)
39
40
tia

41
42
43 Scheme 3: Reaction between poly (amino adamantyl acrylate) (PAm-AdA) and poly
44
l-

45 (glycidyl methacrylate) (PGMA) and formation of hydrogen bonding in the polymer

46
network.
47
48
AC

49
50
51
52
S

53
54
55
56
57
58
59
60
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1
2
3
4
5
6
7
Fo
8
9
10
11
rR
12
13
(b)
14 (a) 14000 2.0
1.6
15
PAdMA R = 0.99904
16 PAdMA 1.9
ev
1.4 PMA -5 -1
Kapp= 6.99 X 10 S 12000 PMA
17 PAm-AdA
PAm-AdA Mntheo = PAm-AdA 1.8
18 1.2 R = 0.99887 10000 1.7
19 -5 -1
Kapp= 4.99 X 10 S
ie
20 1.0 a3 R = 0.99805 8000
1.6
21 -5 -1
Kapp= 1.94 X 10 S

MnGPC
1.5

PDI
0.8
22
ln(1/1-X)

w.
a2 6000
23 1.4
0.6 a1
24 4000 1.3
25 0.4
1.2
26 2000
Co

0.2
27 1.1
28 0.0 0 1.0
29 0 1 2 3 4 5 6 7 8 9 10 11 12 0 10 20 30 40 50 60 70 80
30 Conversion (%)
nf

31 Time (h)
32
33
id

34
35
36 Figure 1: (a) Kinetic plots of ln(1/1-X) versus reaction time t, and (b) the dependence of
en

37
38 the number-average molecular weights (Mn) and molecular weight distributions (PDI =
39
40
Mw/Mn) on the monomer conversion for the atom transfer radical polymerization in bulk
tia

41 at 90°C [M0/CuBr/dNbpy/MBrP, 50:1:1:1]. (▲) Poly (amino adamantyl acrylate) (PAm-

42
43 AdA), (●) Poly (methyl acrylate) (PMA) and (■) Poly (adamantyl methyl acrylate)
44
l-

45 (PAdMA)
46
47
48
AC

49
50
51
52
S

53
54
55
56
57
58
59
60
29
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2
3
4
5
6
7
Fo
8
9
10
11
rR
12
13
14
15
16
ev
17
18
19
ie
20
21
22
w.

23
24
25
26
Co

27
28
29
30
(a) (b) (c)
nf

31
32
33
id

34
35
36
en

37
38
39
40
Figure 2: Solutions of CuBr in amino adamantyl acrylate (Am-AdA) (4 mg/1mL) (a),
tia

41
42
43
CuBr in adamantyl methyl acrylate (AdMA) (4 mg/1mL) (b), and CuBr in methyl
44 acrylate (MA) (4 mg/1mL) (c).
l-

45
46
47
48
AC

49
50
51
52
S

53
54
55
56
57
58
59
60
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2
3
4
5
6
7
Fo
8
9
10
11
rR
12 3.5
13
14
(a) 3.0
30 min (b)
2.5
15 3.0
16 1h
ev
2.0

Absorbance
17 2.5 1.5

18
1.0
19
10 h
ie
20 2.0 0.5

21
Absorbance

0.0

22
w.
1.5 -0.5
23 400 600

24 Wavelength (nm)

25 1.0
26
Co

27 Am-AdA
0.5
28
Am-AdA + CuBr
29
30 0.0
nf

31
32 200 400 600 800 1000
33
id

34 Wavelength (nm)
35
36
en

37 Figure 3: UV-vis Spectra of (a) amino adamantyl acrylate (Am-AdA) (dotted line),
38
39 and mixture of Am-AdA and CuBr (solid line) (both at a concentration of 5.0 x 10-4
40
mol/L in tetrahydrofuran); (b) UV-vis Spectra of the mixture of Am-AdA and CuBr at
tia

41
42
different time.
43
44
l-

45
46
47
48
AC

49
50
51
52
S

53
54
55
56
57
58
59
60
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2
3
4
5
6
7
Fo
8
9
10
11
rR
12
13
14
15
16
ev
17
18
19
ie
20
21
22
w.

23
24
25
26
Co

27
28
29
30
nf

31
32
33
id

34
35
36
en

37
38
39
40 Figure 4: 1HNMR spectra of the polymers (a) Homopolymer of poly (amino adamantyl
tia

41 acrylate) (PAm-AdA); (b) Copolymer of poly (amino adamantyl acrylate-co-poly methyl

42
43 acrylate) (PAm-AdA-co-PMA) (25:75).
44
l-

45
46
47
48
AC

49
50
51
52
S

53
54
55
56
57
58
59
60
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1
2
3
4
5
6 (a)
7 2400
Fo
8
2200
9
10 2000
11
rR
1800
12
13 1600
Counts

14
1400
15
16
ev
1200
17
1000
18
19 800
ie
20 600
21
22 400
w.

23 200
24 1000 2000 3000 4000 5000 6000
25
26 (b) Mass (m/z)
Co

2500
27
COOCH3
28
2400.75522

2621.70147

2842.15904

3063.18259

3947.52332
3505.33096
2179.60906

3284.05153

3726.18836
29
CH3 CH CH2 CH Br
30 2000 11
nf

31
OOC
32
33
1500
id

34
Counts

35
1944.23035

36 NH2
en

37 1000 Structure a
38
39
40 MW = 2621
tia

500
41
42
43
44 0
l-

45 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000
46 Mass (m/z)
47
48
AC

49
50 Figure 5: Matrix assisted laser desorption ionisation time-of-flight mass spectrum of
51
52 poly (amino adamantyl acrylate). (5a) Whole mass spectrum, (5b) Am amplified region.
S

53
54
55
56
57
58
59
60
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2
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4
5
6
7
Fo
8
9
10
11
rR
12 18
13
Mn = 8817
Refractive Index Response (mV)
14 16
15 PDI = 1.35
16
ev
14
17 Mn = 5572
18 12 PDI = 1.33
19
ie
20 10
21
22 8
w.

23
24 6
25
4
26 10 12 14 16 18 20 22
Co

27
Elution time/min
28
29
30
nf

31
Figure 6: Gel permeation chromatography traces of poly (amino adamantyl acrylate)
32
33 macroinitiator and poly (methyl methacrylate-b- poly amino adamantyl acrylate)
id

34
35 prepared by chain extension reaction.
36
en

37
38
39
40
tia

41
42
43
44
l-

45
46
47
48
AC

49
50
51
52
S

53
54
55
56
57
58
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60
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2
3
4
5
6
7
Fo
8
9
10 3382 3230
11
1586
rR
12
13
14 1722
15
Absorbance

16
ev
17
18 (C)
19 1721
ie
20 3320
21
22
w.

23
1722
24
25 (b)
26
Co

27 (a)
28
29
30 4000 3500 3000 2500 2000 1500 1000
nf

31 -1
Wavenumber (cm )
32
33
id

34
35
36 Figure 7: FTIR spectra for (a) Poly (glycidyl methacrylate) (PGMA), (b) Poly (amino
en

37 adamantyl acrylate) (PAm-AdA) and (c) PGMA-PAm-AdA (1:1) (Polymer VI).

38
39
40
tia

41
42
43
44
l-

45
46
47
48
AC

49
50
51
52
S

53
54
55
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58
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1
2
3 (a) (b)
4
5
6
7
Fo
8
9
10
11
rR
12
13
14
15
16
ev
17
18
19
ie
20
21 (c) (d)
22
w.

23
24
25
26
Co

27
28
29
30
nf

31
32
33
id

34
35
36
en

37
38 Figure 8: Field-emission scanning electron micrographs of the samples: Figure (a) Poly
39
40 (glycidyl methacrylate) (PGMA), (b) Poly (amino adamantyl acrylate) (PAm-AdA),
tia

41
42 Figure (c) and (d) Polymer (VI) [PGMA-PAm-AdA] in low and high magnification
43
44 respectively.
l-

45
46
47
48
AC

49
50
51
52
S

53
54
55
56
57
58
59
60
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2
3
4
5
6
7
Fo
8
9
10
11
rR
12
13
14
15
16
ev
17
18
19
ie
20
21
22
w.

23
24
25
26
Co

27
28
29
30
nf

31
32
33
id

34 Figure 9: The optimized 3D-structure of the hydrogen bonded polymer (VI) (as shown in
35
36 Scheme 3).
en

37
38
39
40
tia

41
42
43
44
l-

45
46
47
48
AC

49
50
51
52
S

53
54
55
56
57
58
59
60
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1
2
3
4
5
6
7
Fo
8
9
10
11
rR
12 -1.4 -2
13
14
-3
15 c
16
ev
0
17 -4 Tg = 131 C
18
b
19 a
Heat Flow

-1.6 -5
ie
20 0
21 Tg = 55 C
-6
22
w.
50 100 150 200
23 0
24 Tg = 63 C
25
26 endotherm
Co

27 -1.8 0
103 C
28
29
30
nf

31 25 50 75 100 125 150

32
0
33 Temperature ( C)
id

34
35
36
en

37 Figure 10: Differential Scanning Calorimetric thermogram of (a) Polymer (VI) (as
38
39 shown in Scheme 3); (b) Poly (glycidyl methacrylate) and (c) Poly (amino adamantyl
40
acrylate).
tia

41
42
43
44
l-

45
46
47
48
AC

49
50
51
52
S

53
54
55
56
57
58
59
60
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1
2
3
4
5
6
7
Fo
8
9
10
11
rR
12
13
14
15
16
ev
17
18
19 “Table of Contents Graphic”
ie
20
21
22
w.

23
24
25
26
Co

27
28
29
30
nf

31
32
33
id

34
35
36
Tailor-made Poly(methyl Acrylate) bearing Amantadine Functionality (Amino
en

37
38
39 Adamantyl) via Atom Transfer Radical Polymerization (ATRP); A Precursor of
40
Supramolecular Crosslinked Polymer
tia

41
42 A. Amalin Kavitha, Nikhil K. Singha*
43
44
l-

45
46
47
48
AC

49
50
51
52
S

53
54
55
56
57
58
59
60
39
ACS Paragon Plus Environment