Nghiên cứu tổng hợp rod coil diblock copolymers dẫn điện poly 3 hexylthiophene block poly 2 hydroxyethylmethacrylate random n n dimethylamino 2 ethylmethacrylate trên cơ sở poly 3 hexylthiophene macroinitiator

ỦY BAN NHÂN DÂN TP.HCM SỞ KHOA HỌC VÀ CÔNG NGHỆ BÁO CÁO NGHIỆM THU (Đã chỉnh sửa theo góp ý Hội đồng nghiệm thu) Nghiên Cứu Tổng Hợp Rod-Coil Diblock Copolymers Dẫn Điện Poly(3-hexylthiophene) – block – Poly (2hydroxyethylmethacrylate – random – N,N-Dimethylamino -2ethylmethacrylate) Trên Cơ Sở Poly(3-hexylthiophene) Macroinitiator Chủ nhiệm đề tài: TS Nguyễn Trần Hà Cơ quan chủ trì đề tài: Trường Đại Học Bách Khoa – Đại Học Quốc Gia TP HCM THÀNH PHỐ HỒ CHÍ MINH THÁNG 12/ 2016 TĨM TẮT NỘI DUNG NGHIÊN CỨU K ệ ệ ệ L ệ ệ ệ ệ ệ ặc í í ệ N ệ PSC OFET OLED ấ emmiting diodes), ố ệ PSC ấ OFET PLED ệ ệ gia cơng nhan í T ấ ấ ú x ằ ệ GRIM ệ ấ í ổ ệ í ấ NMR ổ ắ ýG GPC í ú ố í ú ấ 3ấ ú P3HT coil diblock copolymers Các ặ ổ ă S ầ ổ ệ T ệ ệ ệ ặ ặ V ệ ệ ấ í ổ ấ ệ DSC í ấ ổ H ổ FTIR xú í UV- TGA ệ ặ AFM … K ă ặ ệ ệ ệ i SUMMARY OF RESEARCH CONTENT Since the discovery of conducting polymers (or conjugated polymer) (CPs), they become an exciting new class of electronic materials, which have attracted an increasing interest for opto-electronic application in many institute and industrial company They have many advantages, as compared to the non-conducting polymers, which is primarily due to their electronic and optic properties The conjugated polymer can be used in the large of novel application such as organic solar cells (OSDc), OFET ệ OLED … A PSCs,OFETs and PLED are the most promising for future application because of their non-expensive, enable processing and flexible device In this research, we aim the synthesis of Poly(3-hexylthiophene) via GRIM prolymerization where the number average molecular weight and structure of polymers can be controlled Then the end-group of obtained Poly(3-hexylthiophene) will be modified to be the macroinitiator for synthesis of rod-coil diblock copolymers The obtained diblock copolymers in this research were fully characterized about their structure, morphologies, thermal and optical properties via model characterizations such as 1H NMR, GPC, UV-vis, FTIR, DSC, TGA, contact angle measurement, AFM etc Based on our obtained results, we affirm that these diblock copolymers could be useful for advanced electronic application including OSCs, OFETs, and optical sensor ii MỤC LỤC MỤC LỤC iii DANH MỤC HÌNH VẼ VÀ ĐỒ THỊ xii QUYẾT TỐN KINH PHÍ xviii CHƢƠNG 1: TỔNG QUAN VỀ POLYMER DẪN ĐIỆN Cơ ệ 12 Tổ ệ 15 P ệ .16 Tổ ệ N ý ặ K ố 16 18 – BHJ 19 ặ í ấ B ặ ă M ố .20 21 ệ T ặ ắ ệ ệ ệ 24 c devices) 29 1.6 Poly(3-hexylthiophene) .34 C D P P H H D Tổ H P 3-H x ện 35 P ổ M C P ổ R P Tổ 37 G R D 36 C –C D R –C M C D 38 D C ệ T D Cơ Sở P3HT 40 ệ .47 iii 0T Tí Ý 49 ấ 50 í ễ 50 3M 53 CHƢƠNG 2: TỔNG HỢP MONOMER 55 N ệ 2.3 Tổ P í 57 -bromo-3-hexylthiophene monomer 58 P ơ 58 3.3 T 61 K ổ Tổ -bromo-3-hexylthiophene monomer 63 -bromo-3-hexyl-5-iodothiophene monomer 66 P ơ Q 66 ệ T 67 68 K ổ -bromo-3-hexyl-5-iodothiophene monomer 70 K 72 CHƢƠNG 3: TỔNG HỢP POLYMER DẪN ĐIỆN POLY(3HEXYLTHIOPHENE) CẤU TRƯC ĐIỀU HÕA ĐẦU NỐI ĐI (REGIOREGULAR POLY(3-HEXYLTHIOPHENE) 73 3.3 P í 75 Tổ 3- x ầ ố 3- hexylthiophene) (P3HT) 76 P .3 T ơ 76 81 iv K ổ poly(3-hexylthiophene) 82 K FTIR 82 K .3 K GPC 85 K M K UV-vis .87 H NMR 83 .6 K -Tof 86 í ệ DSC 88 K AFM 89 3.6 K L 90 CHƢƠNG 4: BIẾN TÍNH NHÓM CUỐI MẠCH CỦA POLY(3HEXYLTHIOPHENE) 92 Tổ .93 4.2 N P ệ –H 4.4 B ấ 94 í 94 í ố V (Br-P3HT-CHO P P3HT B H B CHO –Haack .95 95 Q ệm 97 T 98 K í ố B H P3HT thành Br/CHO (Br-P3HT-CHO) .98 K FTIR K M 4.6 B B -P3HT-CHO .98 -Tof cùa Br-P3HT-CHO .99 í Br/CH2OH (Br-P3HT-CH2OH ố P3HT B CHO 101 v .6 P ơ Q 101 ệ 6.3 T 103 103 K í ố B CHO P3HT thành Br/CH2OH (Br-P3HT-CH2OH) 104 K FTIR K M 4.8 B B -P3HT-CH2OH 104 -Tof cùa Br-P3HT-CH2OH 105 í ố P3HT B CH2OH 107 Br/CH2OOC(CH3)2Br (P3HT-Macroinitiator) P ơ Q 107 ệ M 108 .108 K í P3HT ố Br/CH2OH B CH2OOC(CH3)2Br (P3HT-Macroinitiator) 109 K FTIR K M K 0K P3HT-Macroinitiator 109 -T P3HT-Macroinitiator 110 H NMR cùa P3HT-Macroinitiator 112 .113 CHƢƠNG 5: TỔNG HỢP DIBLOCK COPOLYMER DẪN POLY(3HEXYLTHIOPHENE)-block-POLY(2-HYDROXYETHYLMETHACRYLATErandom-N,N-DIMETHYLAMINO-2-ETHYLMETHACRYLATE) (P3HT-bP(DMAEMA-r-HEMA)) BẰNG PHẢN ỨNG CHUYỂN ĐỔI GỐC TỰ DO NGUYÊN TỬ (ATRP) 114 Tổ 115 N P ệ –H ấ 116 í 116 vi 5.4 Ph n ng tổng h p copolymer Poly(HEMA-r-DMAEMA) .116 5.4.1 P ơ 116 Q ệ tổng h p copolymer Poly(HEMA-r- DMAEMA) 119 M tổng h p copolymer Poly(HEMA-r-DMAEMA) 119 K ổ P HEMA-r-DMAEMA) 120 5.5 Ph n ng tổng h p diblock copolymer d n poly(3-hexylthiophene)-blockpoly(2-hydroxyethylmethacrylate-random-n,n-dimethylamino-2-ethylmethacrylate) (P3HT-b-P(DMAEMA-r-HEMA)) ph n ng ATRP .121 5.5.1 P ổ P3HT-b-P(DMAEMA-r-HEMA)) 122 5.5.2 Q ệ ổ diblock copolymer ệ P3HT-b- P(HEMA-r-DMAEMA) .122 5.5.3 M tổng h p diblock copolymer ệ P3HT-b- P(HEMA-r-DMAEMA) .123 5.5.4 K FTIR 5.5.5 K 5.6 K copolymer P3HT-b- P(HEMA-r-DMAEMA) 125 H NMR copolymer P3HT-b- P(HEMA-r-DMAEMA) 126 .130 CHƢƠNG 6: SULFONATION P3HT-b-P(DMAEMA-r-HEMA) QUATERNIZATION P3HT-b-P(DMAEMA-r-HEMA) 132 Tổ 133 N ệ –H ấ 6.3 Ph n ng tổng h p Sulfonation Quaternization c a P3HT-b- 133 P(DMAEMA-r-HEMA) 134 6.3 P ổ Sulfonation Quaternization c a (P3HT-b-P(DMAEMA-r-HEMA)) 134 vii 6.3 Q ệ ổ Sulfonation Quaternization c a (P3HT-b-P(DMAEMA-r-HEMA)) 136 6.3.3 M tổng h p ổ p Sulfonation Quaternization c a (P3HT-b-P(DMAEMA-r-HEMA)) 137 6.3.4 K H NMR Sulfonation Quaternization c a (P3HT-b- P(DMAEMA-r-HEMA)) .138 6.4 KẾT LUẬN .140 CHƢƠNG 7: TÍNH CHẤT CỦA SULFONATED P3HT-b-P(DMAEMA-rHEMA) VÀ QUATERNIZED P3HT-b-P(DMAEMA-r-HEMA) 141 7.1 Tổng quan 142 P í 142 7.3 Tính chất hịa tan c a Sulfonated P3HT-b-P(DMAEMA-r-HEMA) quaternized P3HT-b-P(DMAEMA-r-HEMA) 142 7.4 K t qu p xúc c a Sulfonated P3HT-b-P(DMAEMA-r-HEMA) Quaternized P3HT-b-P(DMAEMA-r-HEMA) 145 ổi cấu d ng c a Sulfonated P3HT-b-P(DMAEMA-r- 7.5 Kh o sát s HEMA) Quaternized P3HT-b-P(DMAEMA-r-HEMA) 147 7.6 Tính chất nhiệt c a Sulfonated P3HT-b-P(DMAEMA-r-HEMA) Quaternized P3HT-b-P(DMAEMA-r-HEMA) .150 7.7 K t qu AFM d ện c a Sulfonated P3HT-b-P(DMAEMA-r- HEMA) Quaternized P3HT-b-P(DMAEMA-r-HEMA) 153 7.8 Kh o sát s p c a Sulfonated/Quaternized P3HT-b-P(DMAEMA- r-HEMA) chất nh n electron PCBM 155 7.9 KẾT LUẬN .157 CHƢƠNG 8: KẾT LUẬN VÀ KIẾN NGHỊ 158 TÀI LIỆU THAM KHẢO 164 viii DANH MỤC CÁC KÝ HIỆU, CÁC CHỮ VIẾT TẮT VIẾT TẮT THUẬT NGỮ TIẾNG ANH THUẬT NGỮ TIẾNG VIỆT PT Polythiophene Polythiophen P3HT Regioregular poly(3-hexylthiophene) OPV Organic Photovoltaics P ệ POPV Polymer Organic Photovoltaics P ệ BHJ Bulk Heterojunction Cấ PCE Power Conversion Efficiency Hệ PA Polyacetylen Polyacetylen CPs Conjugated Polymers P MO Molecular Orbital PSC Polymeric Solar Cells P HOMO Highest Occupied Molecular Orbital M ă LUMO Lowest Unoccupied Molecular Orbital M ă D Donor C ấ A Acceptor C ấ VOC Open circuit Voltage T JSC Short-circuit Current Density C ò FF Fill Factor Hệ ố ầ EQE External Quantum Efficiency Hệ EB Exciton Binding energy Nă IE Ionized Energy Nă EA Electron Affinity Tí poly(3-hexylthiophene) ấ ú ị ú ă ệ ệ polymer ấ ấ ấ ệ ệ ệ x ệ ix CHƢƠNG 8: KẾT LUẬN VÀ KIẾN NGHỊ 158 159 K ă ý ổ ổ > P3HT ấ ú ố ò > P3HT % % ệ GRIM hồn tồn T P3HT í ầ ệ T í ặ ệ P3HT ấ ổ ấ Rod-coil diblock copolymer P3HT-b-P(DMAEMA-r-HEMA) ằ ă ệ ATRP ú ố Hơ í P3HT-b-P(DMAEMA-r-HEMA) -diblock sulfonated P3HT-b-P(DMAEMA-r-HEMA) quaternized P3HTb-P(DMAEMA-r-HEMA) H ệ ấ ố ầ ũ í 0% C ấ í ệ C block copolymers sulfonated P3HT-b-P(DMAEMA-r-HEMA) quaternized P3HT-b-P(DMAEMA-r-HEMA) ệ õ xú o P(DMAEMA-r-HEMA) o r-HEMA) xú P3HT-b-P(DMAEMA- ệ P3HT-b- sulfonated P3HT-b-P(DMAEMA-r4 x 10-10 S/cm HEMA) quaternized P3HT-b-P(DMAEMA-r-HEMA) ầ x 10-10 S/cm Các Diblock copolymers sulfonated P3HT-b-P(DMAEMA-r-HEMA) quaternized P3HT-b-P(DMAEMA-r-HEMA) ố ấ í ệ ũ ă PCBM N ằ ệ ệ ệ ơ ệ ấ ặ -coating hay 160 Hệ ệ ấ ú Trong giai ệ ú ệ ệ (electrochromic devices) C ệ ắ ệ ú - Prof Xavier Crispin, Department of Science and Technology, Division of Physics and Electronics, Organic Electronics Linköping University, Sweden - Prof Prof Tsutomu Yokozawa, Kanagawa University, Japan 161 K ý ă  SẢN PHẨM KHOA HỌC VÀ CÔNG NGHỆ DẠNG KẾT QUẢ III, IV T Đ ng k T Đạt đƣợc bà ă í ă í ố ISI ố ệ 19/01/2016 í ệ ấ C ấ  SẢN PHẨM KHOA HỌC VÀ CÔNG NGHỆ DẠNG KẾT QUẢ I, II TT T Số C ỉ - ỹ ( ă Monomer 2- 5g - ỹ ( tinh t  97% (1H NMR) bromo-3-hexyl- C ỉ ý ) Số ) 50 g, tinh t  98% (1H NMR) 5-iodothiophene P 3- 5g x tinh t  % ấ P3HT ú ố tinh t  % ấ % 1H ò HT > 10 g, ú % 1H ò HT > NMR) NMR) B H P3HT ố 5g g, > % > % 162 (1H NMR) Br/CHO P3HT 5g g, ố > % > (1H NMR) Br/CH2OH P3HT- (1H NMR) (1H NMR) 4g g, M > % > 7% (1H NMR) ố % (1H NMR) Br/CH2OCOC(C H3)2Br Diblock 2g tinh t  tinh t  1.5 g, copolymers 97%, Mn = 7000- 97%, Mn = 10000- (P3HT-b- 12000 g/mol (1H 12000 g/mol (1H NMR P(DMAEMA-r- GPC NMR GPC HEMA)) Inonic diblock 1g tinh t  1.5 g, tinh t  copolymers 97% XRD,1H 97%, 1H NMR, UV- (P3HT-b- NMR Vis P(DMAEMA-r- M HEMA))-PCBM Quaterization t 80% M Sulfonation t 95% 163 TÀI LIỆU THAM KHẢO (1) Skotheim, T A.; Reynolds, J R Handbook of conducting polymers, third edition, Vol 1; Taylor & Francis, 2007 (2) 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