Nghiên cứu tổng hợp các Polyme Acrylat khúc xạ quang hữu cơ đa chức năng với những đơn vị chứa nhóm Diphenylhydrazon được gắn vào nửa Triethylamine hoặc Carbazole

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Hai polyme acrylate khúc xạ quang đa chức năng mới là polydiphenylhydrazone triphenylamine methylacrylate 1.5 và polydiphenylhydrazone carbazole ethylacrylate 2.7 đã được tổng hợp để nghiên cứu khả năng dẫn quang và quang không tuyến tính của chúng trong vật liệu polyme composit khúc xạ quang. Những monome đa chức năng đã thu được bằng phản ứng ngưng tụ giữa phân tử diphenylhydrazine với một cấu tử chuyển điện tích là các dẫn xuất của hoặc triphenylamine hoặc carbazole. Phản ứng polyme hóa được tiến hành sử dụng chất khơi mào AIBN. Cấu trúc các sản phẩm phản ứng được khẳng định bằng các phương pháp phổ (1)H, (13)C-NMR và FAB-MS.

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Nội dung Text: Nghiên cứu tổng hợp các Polyme Acrylat khúc xạ quang hữu cơ đa chức năng với những đơn vị chứa nhóm Diphenylhydrazon được gắn vào nửa Triethylamine hoặc Carbazole

Tieu ban: cdc chdt co hogi linh sinh hqc ISBN: 978-604-913-012-0 SYNTHESIS OF NEW MULTIFUNCTIONAL PHOTOREFRACTIVE ACRYLATE POLYMERS WITH UNITS CONTAINING DIPHENYLHYDRAZONE GROUP ATTACHED TO TRIPHENYLAMINE OR CARBAZOLE MOIETY NGHIEN Ciru TONG HOP CAC POLYME ACRYLAT KHUC XA QUANG HLTU CO DA CHlTC NANG V 6 l NHLTNG DON VI CHlTA NHOM DIPHENYLHYDRAZON DlTOC GAN VAO NlTA TRIETHYLAMINE HOAC CARBAZOLE Nguyen Quoc Vuong, Tran Van Sung Institute of Chemistry (VAST) 18 - Hoang Quoc Viet, Cau Giay, Ha Noi Email: nguvenvh62(fl),gmail.com Abstract: TM:O new tnultifunclional photorefractive acrylate polymers such as polydiphenylhydrazone Iriphenylamine melhylacrylale 1.5 and polydiphenylhydra-zonecarbazole ethylacrylale 2.7 were synthesized for investigation on their photoconducting (PR) and nonlinear optical (NLO) ability in photorefractive polymer composite. The multifuncdonal monomers were obtained by condensation reaction between diphenylhydrazine with a charge transfer compound as Iriphenylamine or carbazole derivatives. The polymerization was carried out using AIBN as initiator. The reaction products structure was confirmed by 'H, '^C-NMR and FAB-Mass spectroscopy. Tom tat: Hai polyme acrylate khiic xd quang da chirc ndng m&i Id polydiphenylhydrazone Iriphenylamine melhylacrylale 1.5 vd polydiphenylhydrazone carbazole ethylacrylale 2.7 dd dugc tdng hgp di nghien ciru khd ndng ddn quang vd quang khdng tuyen linh ciia chiing trong vdt lieu polyme composit khiic xg quang. Nhirng monome da chirc ndng dd thu dugc bdng phdn irng ngirng lu giira phdn tu diphenylhydrazine v&i mdl cdu tu chuyin dien lich la cdc ddn xudt ciia hodc Iriphenylamine hodc carbazole. Phdn irng polyme hda dugc liin hdnh su dung chdt khai mdo AIBN. Cdu true cdc sdn phdm phdn irng dugc khdng dinh bdng cdc phuong phdp phd H, C-NMR vd FAB-MS. I. Introduction Polymeric photorefractive materials, reported for the first time in 1991 [1], have a variety of important applications in the field of high-density optical data store, holographic image processing techniques and programmable optical interconnection [2, 3, 4]. To gain photorefractive effect, the material has to possess photoconductivity and optical nonlinearity simultaneously. These properties are exhibited in two types of polymeric materials: one is fully functionalized photorefractive polymers [5-7] and the other is host-guest polymeric systems [8-10]. However, both approaches still have significant drawbacks. While the former requires elaborate synthesis, the latter often faces problems due to phase separation. To harmonize both these problems, host-guest systems consisting of multifunctional photorefractive polymers which possess both photoconductive and electro-optic properties, 172 Hoi nghi Khoa hqc ky- niem 35 ndm \ 'ien Khoa hqc vd Cong nghe Viet Nam - Hd Noi 10/2010 have been also reported [11-14]. The multifunctional photorefractive polymers are easier in synthesis and exhibit higher stability. As well known, the carbazole and triphenylamine (TPA) are good charge (hole or electron) transporting materials, on the other hand, diphenylhydrazine compounds are nonlinear optical chromophores. In continuation of our work on photorefractive polymers [9, 13, 15-17], we here report the synthesis of two new multifunctional acrylate polymers with units containing diphenylhydrazone group attached to triethylamine or carbazole moiety Experimental Materials and instruments: All reagents were purchased from Aldrich Chem. Co. or TCI Chem. Co.. The solvents for reactions were dried then distilled before use. The products were purified by column chromatography (CC) on silica gel 60 (Merck Co.). All reactions were carried out under dried nitrogen or argon atmosphere. The ' H , ' ^ C - NMR spectra were operated on a Varian Mercury 400MHz. FAB-MS was measured on a JEOL JMS700 (high resolution). N,N-bis[(4-formyl)phenyl]-N-phenylamine(l.l). The formylation of TPA (50mmol, 12.25g) was can-ied out by common procedure using Vilmeier reagent. The reaction product was isolated by chromatography column (cc) to give a yellow product 4.1 in 65% yield. ll 'H-NMR(CDCl3): 9.9(s, 2H) of 2x CHO, 7.78(d, 4H), 7.4(t, 2H), 7.3(t, IH) and 7.22- 7.45(m, 6H) of aromatic proton. '^C-NMR(CDCl3): 190.78(2xCHO), 152.23(2xC-N) 145.80(C-N), 131.55, 131.48, 130.4, 127.30, 126.51, 122.98 N-(4-formyl)phenyl-N-(4-hydroxymethyl)phenyl-N-phenylamine(1.2). One of both formyl groups of compound 1.1 was reduced into hydroxymethylene group by reagent NaBH4 in suitable molar ratio. The reaction product was purified by cc to give a white solid product 1.2 in 85% yield. 'H-NMR(CDCl3): 9.8(s, IH) of CHO, 7.67(d, 2H), 7.48-7.46(m, 4H), 7.6-7.2(m, 5H), 7.2-7.0(m, 2H) of aromatic proton, 4.68(s, 2H) of CH2-0.'^C-NMR(CDCl3): I90.83(CHO) I53.63(C-N), 146,38(C-N) 145.87(C-N), 138.04, 131.65, 130.08, 129.43, 128.82, 126.60, 125.50, 119.70,65.08. N-(4-diphenylhyrazonomethyl)phenyl-N-(4-hydroxymethyl)phenyl-N- phenylamine (1.3) The condensation between aromatic aldehyde 1.2 and diphenylhydrazine hydrochloride was carried out in solvent mixture of DCM and ethanol using TEA catalyst at reflux for lOhs. The reaction product was purified by CC to afford a page yellow pure product 1.3 in 85% yield. 1, 'H-NMR(CDCl3): 7.47(d, 2H), 7.44-7.38(m, 4H), 7.27-7.0(m, I8H) of aromafic proton, 4.64(d, 2H) of CH2-O, 1.64(t, IH) of OH. '^C-NMR(CDCl3): 147.65, 147.34, 147.04 143.71, 135.38, 135,33, 130.38, 129.74, 129.28, 128.28, 127.16, 124.50. 124.35, 124 32' 123.45,123.14,122.44,65.03. N-(4-acr>loyloxymethyl)phenyl-N-(4-diphenyIhyrazonomethyI)phenyl-N-phenyl- amine] (1.4) To a solution of compound 1.3(5.6g. 12mmol), 2,6-di-/-butyl-4-methyl phenol (4mg) and TEA (2.78 ml, 2.02g. 20mmol) in tetrahydrofurane (THF)(75ml). a solution of acryloyl chloride (1.6ml, 1.8g, 20mmol) in THF(lOml) was added at 0° C then the reaction mixture 173 Tiiu ban: cdc chdl co hogt tinh sinh hqc ISBN: 978-604-913-01 J-u was warmed to room temperature and stirred overnight. Water was added and the mixture was extracted with etylacetate. The extract was washed with water, dried over Na2S04. evaporated. The obtained residue was separated by CC using n-hexane:DCM (3.5:1.5) as eluent solvent to give 2.5g of product 1.4 in 46% yield. 'H-NMR(CDCl3) 7.49(d, 2H), 7.43-7.38(m, 4H) and 7.28-7.0(m, 18H) of aromatic proton, 6.45(d, IH). 6.2-6.14(m, IH) and 5.85(d, IH) of vinyl group. 5.14(s, 2H) of CH2-O. %NMR(CDCl3): 166.2(CO), 147.92, 147.81, 147.63, 144.02, 135.60, 131.40, 139.98, 130.19, 130.07, 129.90, 129.65, 128.67, 127.51, 125.08, 1124.67, 124.08, 1233.70, 122.76, 66.42. Poly[N-(4-acryloyloxymethyl)phenyl-N-(4-diphenyIhyrazonomethyl)phenyI-N- phenyl-amine](1.5) A solufion of monomer 1.4(2.4g, 4.6mmol) and 2,2'-Azobis-isobutyronitriIe(AIBN) (22,7mg, 0,I38mmol) (3mol% to the monomer) in THF was placed in a glass ampoule. The solution was degassed by freeze-vaeuo-withdraw cycles for three times then heated the sealed ampule at 60°C with stirring for 2 days. Product was purified by precipitate from MeOH three fimes then dried in vacuo at 30°C overnight to give 1.4g of pale yellow pure product 1.5 in 58% yield. 'H-NMR(CDCl3): 7.5-6.7(m, br) of aromatic proton and N-vinyl proton, 4.82(brs) of CH2-O, 2.6-1.0 (m, br) of backbone proton (-CH-CH2-). 2-[9-(2-hydroxy)ethyl-9//^-carbazol-3-yl-]methylene-l,l-diphenylhydrazone(2.5) Compound 2.5 was obtained by common condensation between aromatic aldehyde 2.4 and diphenylhydrazine hydrochloride.The reaction product was purified by cc to give yellow solid pure product 2.5 in 75% yield. ' H - N M R ( C D C 1 3 ) : 8.19 (s, IH), 8.06 (d, IH) and 7.85(d, IH) of carbazole, 7.5- 7.15(m, 14H) of carbazole and two phenyl group, 4.4 (t, 2H) and 4.9(td, 2H) of 9-ethyl group, 1.59 (t, IH) of OH. '^C-NMR(CDCl3): 143.98, 140.81, 137.07, 129.76, 127.78, 125.96, 124.26, 1124.20, 123.07, 122.98, 122.55, 120.46, 119.46, 118.89, 108.99, 108.95, 61.38, 45.50. 2-[9-(2-acr>Ioyloxy)ethyl-9fl'-carbazol-9-yl-3-yI]methylene-l,l- diphenylhydrazone(2.6 ) The reaction was carried out as above aerylation procedure. The reaction product was isolated by cc to give yellow pure product in 55% yield 'H-NMR(CDCl3): 8.2 (s, IH), 8.07 (d, IH) and 7.89(d, IH) of carbazole, 7.5-7.3 and 7.28-7.17(m, 14H) of carbazole and two phenyl group, 6.25 (d, IH ), 6.0(dd, IH) and 5.7(d, IH) of vinyl group, 4.59(t, 2H) and 4.55(t, 2H) of 9-ethyl group. '^C-NMR(CDCl3): 165.87(00), 143.97, 140.67, 14-.6I, 137.02, 131.59, 129.75, 127.87, 127.74, 125.96, 124.20, 123.16, 123.09, 122.55, 120.52, 119.56, 118.98, 108.79, 108.69,62.29,41.75. Poly{2-[9-(2-acryloyloxy)ethyl-9//-carbazol-9-yl-3-yI]methyIene-l,l- diphenylhydrazone} (2.7) The polymerization was performenced as above polymerization procedure. The polymeric product was purified by precipitated from MeOH for three times to afford pale yellow pure polymer 2.7 in 54% yield. 1H-NMR(CDC13): 8.2-6.6 (aromatic proton), 4.6-3.89(ethyl group), 2-0.7(backbone proton -CH-CH2-). 174 Hoi nghi Khoa hqc ky niem 35 ndm Vien Khoa hqc vd Cong nghe Viet Nam - Hd NqilO/2010 Results and discussion To obtain the multifunctional acrylate polymers we carried out the condensation reaction between diphenylhydrazine and derivatives of triphenylamine or carbazole. The synthetic routes were shown in scheme 1 and scheme 2. Polymer 1.5, with units comprise triphenylamine molecule attached diphenylhydrazone moiety, was obtained after 5 steps (scheme 1). The formylation of triphenylamine using excessive amount(12eqv) of Vilmeier reagent to prepare dialdehyde 1.1 in 45% yield. The signals at 5H 9.90 and 5c 190.78 ppm on NMR spectra showed the presence of aldehyde groups. Next step is reduction of one of both aldehyde groups by NaBH4 in a suitable mol ratio to give compound 1.2. The NMR spectra showed both signals of aldehyde group at 5H 9.80, 5c 190.78 and CH2-OH group at 5H 4.68, 5c 65.08ppm. The condensation reaction was conveniently carried out between diphenylhydrazine and aldehyde group of compound 1.2 to afford muhifunctional product 1.3 in high yield (85%). On the ' H-NMR spectra, the signal of aldehyde group dispeared and appear new overlapped signals of diphenyl group at aromatic area (5H 7,27-7,00), the integrant values of proton signals OHC NHp HCI EtaN, 85% Scheme 1: Synthesis of poly diphenylhydrazone triphenylamine methyl acrylate (1.5) increasing suitable with proton number of condensation product and the appearance of new signals on the C-NMR spectra confirmed the condensation. Step 4 is the esterificafion of alcohol group of compound 1.3 by acryloyl chloride to give acrylate monomer 1.4. The NMR spectra of this acrylate monomer indicated signals of arylic group at 5H 6.45 (d, I Ha) and 5.85(d, IHb) of vinyl (C=CH2) group and 5c 166.20 of C=0 group. The FAB-Mass spectrum of this monomer gives a molecular ion peak at m/z 523 [M]* (100). Finally, the polymerization of monomer 1.4 was carried out by a free radical method using AIBN as an initiator for two days to afford acrylate polymer 1.5. On the ' H-NMR spectrum of the polymer 1.5 the proton signals of vinyl group disappeared and the appearance of broad signal at 5H 7.44-6.60 ppm of aromatic protons, a broad signal at 5H 4.82 of CH2-O protons and broad peaks at 5ii 2.20-1.20ppm confirmed a success of the polymerization. 175 Tiiu ban: cdc chdt co hogt tinh sinh hqc ISBN: 978-604-913-012-0 TEA/THF 55% Scheme 2: Synthesis of poly diphenylhydrazone carbazole methyl acrylate (2.6) Compound 2.7 was synthesized through 7 steps (scheme 2). From step 1 to step 4, these reactions were carried out with the same procedures as in reference [12] to give N-(2- hydroxyethyl)-9/7-carbazole-3-carbazaldehyde 2.4. The signals of compound 2.4 on NMR spectra indicated the presence of a CHO and CH2-OH group (5H 9.79, 5c 190.83 and 5H 4.68, 5c 65.0). The continuous condensation between aldehyde and diphenylhydrazine gives a multifunctional compound 2.5. The appearance of new signals at aromatic area on H, C- NMR spectra of this product confirms that the diphenylhydrazone moiety is attached to the carbazole moiety. The next step is the aerylation reaction of compound 2.5 to give monomer 2.6. On H, C-NMR spectra of compound 2.6, the new signals of acrylic group appeared at 5H 6.25(d, IHa), 6,00(d, IHb), 5.70(d, IH) and and 5c 165.87 ppm. The FAB-Mass spectrum gives a molecular ion peak at m/z 459[M]"^(100). The polymerization of 2.6 also gives expectative polymer 2.7. 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