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Microstructure Characterization of Poly(2-N-Carbazolylethyl Acrylate) by Two-Dimensional NMR Spectroscopy

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Microstructure Characterization of Poly(2-N-Carbazolylethyl Acrylate) by Two-Dimensional NMR Spectroscopy Indian Journal of Chemistry Vol. 44A, January 2005, pp. 58-63 Microstructure characterization of poly(2-N-carbazolylethyl acrylate) by two-dimensional NMR spectroscopy _A S Brar*, M Markanday & S Gandhi Department of Chemistry, Indian Institute of Technology, Delhi, New Delhi 11001 6, India Email : asbr;[email protected]~t.in - ~ Received 8 Septelllber 2004; re vised 15 October 2004 Poly(2-N-carbazolylethyl acrylate) has been synthesized by solution polymerization of 2-N-carbazolyethyl acrylate with 2,2'-azobisisobutyronitrile as free radical initiator. Di stortionless Enhancement by Polarization Transfer has been used to di stingui sh between the overlapping main -chain methine and side-chain methylene resonances in DC { I H } NMR spectrum . Configurational assignments of carbon and proton reso nances of main-chain methylene group have been done using two-dimensional Heteronuclcar Single Quantum Correlation spectroscopy and two-dimensional Tot,ti Correlation Spectroscopy. Two and three bond order carbonlproton couplings have been in vesti gated using Heteronuclear Multiple Bond Correlation studies. 7 IPC Code: Int. C1. : C08F 120118; GOIR 33/20 Homo- and co-polyacrylates are of academic and relationship I3.14. High-resolution one-dimensional and industrial interest because of their wide range of two-dimensional NMR spectroscopy have proved to physical and chemical properties that can be be one of the most informative and revealing controlled by an appropriate choice of pendant group techniques for the investigation of polymer . 15·19 in the polymer and design of copolymer structure. microstructure . Much work has been done to study Poly(2-N-carbazolylethyl acrylate) belongs to the the photoconductive properties of poly(2-N­ class of photoconductive polymers 1.3 , which finds carbazolylethyl acrylate) and its copolymers. widespread application in electrophotography, light­ However, a literature survey reveals that the 45 emitting diodes, photorefractive materials . and microstructure of this polymer has not been reported 6 7 photovoltaic devices . The photoinduced intrachain in detail. charge transfer complexes in a photoconductive polymer ensure efficient charge transport across the In this paper, we report the microstructure of polymeric materials. Most investigations have poly(2-N-carbazolylethyl acrylate). Unambiguous concentrated on search for a chromophore that has a assignments have been made with the help of hi gh efficiency in forming such charge-transfer I3C{ IHI NMR, distortion less enhancement by complexes. Higher carrier mobility can be expected in polarization transfer (DEPT), 20 heteronuclear polymers where the chromophore is directly linked to single-quantum correlation (HSQC), total correlation th e backbone despite the fact that molecular mobility spectroscopy (TOCSY) and 20 het ronuclear multi of the chromophore in such cases will be depressed. bond correlation (HMBC) NMR experiments. This insight has given impetus to further research on design of photoconductive polymers in which Materials and Methods chromophores are directly linked to main chain lJ 11 Carbazole (96%, Aldrich) was recry stallized from through chemical bonding • . Poly(2-N­ methanol. Ethylene carbonate (98 %, Aldrich) and carbazolylethyl acrylate)'2 is an example of sodium hydride (50% oil dispersion, CDH Pvt. Ltd., photoconductive polymer in which the carbazole New Delhi) were used as supplied. Acryloyl chloride moieties appear as pendant groups along the main (98 %, Aldrich) was distilled under reduced pressure chain of the polymer. and stored at low temperature. AIBN (Fluka) was The determination of microstructure in polymers is recrystallized from methanol and stored at low useful for establishing the structure-property temperature. BRAR et at.: MICROSTRUCTURE CHARACTERIZATION OF POLY(2-N-CARBAZOLYLETHYL ACRYLATE) 59 Procedure by solution polymerization using AIBN (0.05 mol %) Synthesis of monomer, 2-N-carbazolylethyl acrylate initiator in distilled toluene at 60°e. The A solution of carbazole (10 g, 0.06 mol) and 4.32 g homopolymer was precipitated in methanol. Further (0.072 mol) sodium hydride in dry tetrahydrofuran purification was done by reprecipitation in CHCI3/ (THF) was vigorously stirred at O°e. After 2 hours of CH30H solvent system. stirring ethylene carbonate (6.38 g, 0.072 mol) was slowly added and the mixture was stirred at O°C for NMR studies 30 min. and then at 40°C for three hours. To the NMR experiments were performed in CDCI 3 on resulting solution ice-cold water was added gradually, Bruker 300 MHz DPX spectrometer at a frequency of followed by stirring at 40°C for 3 hours. Finally, 300.13 MHz and 75.5 MHz for 'H and I3C {'H} NMR work-up of the reaction mixture was done by pouring respectively using the standard pulse sequences as 2o 2 200 ml of water and extracting the aqueous mixture reported in our earlier publications . ' . with dichloromethane (200 ml x 3). The extract was chromatographed on a silica-gel column. (75:25/ Results and Discussion hexane: ethyl acetate) (Scheme I). [M. pt. 81-81.5°C J3C{'H} NMRstudies 13C{ 'H} NMR spectrum of poly(2-N- (Lit M. pt. 83-83.5°C). 'H NMR (in CDC b) 81.35 (s, carbazolylethyl acrylate) with assignment of various IH, OH), 3.80-3.82 (t, 2H, NCH2), 4.20-4.24 (t, 2H, resonance signals, is shown in Fig. I. The carbonyl OCH2), 7.00-7.90 (m, 8H, aromatic)]. A solution of acryloyl chloride (5.1 g, 0.057 mol) carbon resonates at 8173.25-174.5 ppm showing in 20 ml of dry DCM was added dropwise under sensitivity towards configuration. The signals around vigorous stirring to a mixture of 2-N-(hydroxyethyl) 8173.25-173.75, 8173.75-174.25 and 8174.25-174.5 carbazole (10.0 g, 0.047 mol) and 20 ml triethylamine ppm are assigned to mm, mr/rm and IT triads in 200 ml of dry DCM. The mixture was stirred respectively. Carbons 3, 5 and la of the carbazole ring in the homopolymer were erroneously assigned by overnight at O°e. After the Et3N.HCI was filtered off 22 at room temperature, the residue was Crone and Natansohn . Correct assignments of the carbazole ring in poly(N-vinylcarbazole) were chromatographed on a silica gel column (7:3lhexane: 23 ethyl acetate). [M.pt. 76°C (lit. M.pt. 75-76°C). 'H reported by Dias et al. The aromatic carbons of the pendant group in the investigated poly(2-N­ NMR (in CDCI3) 84.50-4.60 (m, 4H, OCH2CH2N), carbazolylethyl acrylate) have been assigned on the 5.80-6.30(m, 3H, CH =CH-), 7.00-7.90(m, 8H, 2 basis of investigations reported by Dias et at. The aromatic)]. aromatic carbons were found to resonate at 8108.5(C- Polymerization 2), 8118.0 (C-l), 8119.0 (C-4), 8122.0 (C-4a), Poly (2-N-carbazolylethyl acrylate) was prepared 8124.5(C-3) and 8141.0 (C-Ia) ppm. The -OCH2 yH 20H 1)NaHITHF alOe C/3hrs yH2 b)40oC/2hrs N 2)Ethylene carbonate a}OoC/1 -------1o:D-..-:: I 3)Water(O°C} a)40oC/3hrs ~ ~ carbazole ethylene carbonate 2-N-hydroxyethyl carbazole CH20HI f H2,OCC£H-CH2 ~H2 1)Hydroquinone, tnethyl amine/dry CH2CI2 yH2 ~ ~ + H C=CHCOCI (OoC/overmght) CCDN -..-:: I 1 2 - 1 1 ~ h- 2)Acryloyl chlonde h- ~ 2·cc:oN·hydroxyethyl carbazole acryloyl chlonde 2-N·carbazolylethyl acrylate Scheme I-Synthesis of 2-N-carbazolylethyl acrylate. 60 INDIAN J CHEM, SEC A, JANUARY 2005 mr/rm 1a 2 {'\ " ---,- ~~.- -----.,-....... 4. _-.----,--- .. _ 175 174 173 >c=o {'\ -, ppm 160 140 120 100 BO 60 40 20 Fig. I-The DC{ 'H} NMR spectrum of poly(2-N-carbazolylethyl acrylate). carbon of the side chain appears as a singlet around 862.5 ppm indicating that it is not sensitive to configurational sequence of the homopolymer. 1 'I- ----------- . ~ , The spectral region around 838.8-42.1 ppm is overlapped and can be assigned to backbone methine (-CH) carbon and -NCH2 carbon of the side chain. [ The overlapped carbon regions can be resolved with o~ the assistance of a DEPT-135 spectrum. The m m backbone methy lene (-CH2) carbon appears as multiplets around 832.2-38.8 ppm, indicating its 40 sensitivity towards various configurational sequences. <.CH This region appears as a broad signal due to the bulky pendant group. ppm . ~, ~,~, ~,-,,~~, -I~--o--r- · _r___r-~.,..---,--,- 2-D HSQC NMR studies ppm 2.0 ; .5 1.0 Investigation of the HSQC spectrum facilitates complete assignment of the 'H NMR spectrum. The Fig. 2-The expanded HSQC spectrum showing the methine and p-methylene region of the polymer. expanded aliphatic rer; ion of the HSQC spectrum is shown in Fig. 2. The methine group appears as a cross ppm are assigned to the meso (m) dyad (a and b) and peak centered at 841.13/1.87 ppm. It does not show the cross peak around 8 34.27/1.06 ppm is assigned to any kind of configurational sensitivity. The spectral the racemic (r) dyad of the methylene region, region from 832.3-38.8/0.7-1.5 ppm represents the p­ respectively. methylene group. This group shows sensitivity to The aromatic region is overlapped in the 'H NMR various configurational sequences. The meso spectrum. The protonated aromatic carbons of the configuration of dyad gives two crosspeaks due to carbazole ring can be resolved with the help of two methylene protons having different environment expanded aromatic region of the HSQC spectrum. and the racemic configuration gives one crosspeak in Hence, peaks centered at 8108.5/7.1, 8119/1.7, between these two crosspeaks. The methylene protons 811817.8 and 8124.517 .2 ppm can be assigned to (C- of r dyad and m dyad are depicted in Scheme 2. The 2)-(H-2) [II] , (C-4)-(H-4) [IV], (C-l)-(H-I) [I] and cross peaks around 8 34.2411.28 and 8 34.28/0.74 (C-3)-(H-3) [III] respectively as shown in Fig.
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