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研究生:彭康貞
研究生(外文):Kang-Jen Peng
論文名稱:以原子轉移自由基聚合法合成聚苯乙烯-C60混成材料及其自組裝行為研究
論文名稱(外文):Preparation of polystyrene-C60 hybrid materials through atom transfer radical polymerization (ATRP) and their self-assembled behavior.
指導教授:劉英麟
指導教授(外文):Ying-Ling Liu
學位類別:碩士
校院名稱:中原大學
系所名稱:化學工程研究所
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2010
畢業學年度:98
語文別:中文
論文頁數:145
中文關鍵詞:聚苯乙烯自組裝C60ATRP
外文關鍵詞:C60PSATRPself-assembled
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本研究利用原子轉移自由基聚合(ATRP)合成聚苯乙烯(PS)與碳奈米球(C60)的多段共聚合物,包括PS - C60、PS - C60 - PS、PS - C60 - PS - C60以及C60 - PS - C60、PS18 - C60 - PS - C60 - PS18、PS177 - C60 - PS - C60 - PS177、C60 - PS117 - C60 - PS - C60 - PS117 - C60等二系列。除了以凝膠滲透層析儀(Gel Permeation Chromatography, GPC)、傅利葉轉換紅外線光譜分析儀(Fourier Transform Infrared Spectrometer, FTIR)和紫外光光譜儀(UV-vis spectroscope,UV-vis)鑑定所合成的PS/C60多段共聚合物外,並將其溶於溶液中,以高解析穿透式電子顯微鏡(High Resolution Transmission Electron Microscopy, TEM)和掃描式電子顯微鏡(Scanning Electron Microscopy, SEM)觀察其自組裝的行為。將反應得到的C60-高分子混合材料溶解於氯仿及氯仿/甲醇混合溶液中,旋轉塗佈在矽晶圓及滴在銅網上,在電子顯微鏡的觀測下,自組裝形成奈米環及球的構形,且得到的環及球大小不均一。但在SEM下觀察Br-PS251-Br與C60形成之Polystyrene-C60混成材料,發現受PS長鏈的影響,其於矽晶圓上形成薄膜,進而影響了表面構型,因此Br-PS251-Br與C60形成之Polystyrene-C60混成材料於SEM下,幾乎無法觀察環狀構型。

Poly(styrene) and C60 nanohybrids have been prepared through sequential atom transfer free radical polymerization (ATRP). Two series of samples have been prepared. One series has three samples of PS-C60, PS-C60-PS, PS- C60-PS-C60, and the other has another three samples of C60-PS-C60, PS177-C60-PS-C60-PS177, C60-PS117-C60-PS-C60-PS117-C60. The samples have been characterized with Fourier transform infrared, gel permeation chromatography, ultraviolent-visible spectroscopy, and thermogravimeteric analyzer. The self-assembly behaviors of the prepared samples have also been investigated with scanning and transmission electron microscopy. The samples self-assemble into nano-toroids and nanospheres in chloroform and in the mixed solvent of chloroform/methanol (1/1 v/v).

中文摘要………………………………………………..…..…….………I
英文摘要………………………………………………..………..…….……..……II
致謝………………………………………………………………………………III
目錄……………………………………….……….….……...…...….……………IV
圖目錄………………………………...…...……………...….…………………..VII
表目錄………………………………………..………………………...……..…XIX

第一章 緒論……………………..…………….……………….……..1
1-1 前言…………..………………..………….…………..………………...…1
1-2 C60之製備方法…………………………..…….…………………………..5
1-3 對C60進行表面改質之方法………………………………………...…….7
1-4 原子轉移自由基聚合法 ( Atom Transfer Radical Polymerization,ATRP)9
1-5 研究目的 ……………………….……………...…….….………...…….12

第二章 文獻回顧:碳奈米球(C60)表面共價鍵結………………13
2-1 碳奈米球(C60)與Azide group反應.……………………….…….13
2-2 以陰離子聚合反應合成高分子-C60混成材料…………………………27
2-3 碳奈米球(C60)表面環化加成(cycloaddition)反應………………40
2-4 碳奈米球(C60)表面ATRP反應……………………………………48

第三章 實驗部份…….……………………...…………………...................….63
3-1 實驗藥品…..………..……….……………………….………………..…63
3-2 實驗儀器......…..……………………..…….………………………….…63
3-3 單體及聚合物的合成...……….……………………...……………….…65
3-3.1具有末端-Br官能基之Polystyrene(PS76-Br)之製備…………...65
3-3.2具雙端-Br官能基之Polystyrne(Br-PS251-Br)之製備….......……66
3-4 高分子改質C60表面……………..........………………….....………...…67
3-4.1 PS76-Br改質C60表面系列…………………………..……...….…67
3-4.1.1製備PS76-C60…….……….…………………...……67
3-4.1.2製備PS76-C60-PS115……...……….……………...……68
3-4.1.3製備PS76-C60-PS115-C60…….……….………...…...……69
3-4.2 Br-PS-Br改質C60表面系列…………..……….…...………….…70
3-4.2.1製備C60-PS-C60……………………...…………………...70
3-4.2.2製備PS18-C60-PS-C60-PS18………...………………..……71
3-4.2.3製備PS177-C60-PS-C60-PS177….……..…………………....72
3-4.2.4製備C60-PS177- C60-PS-C60-PS177-C60………………….…73

第四章 結果與討論……………………………………………….…………74
4-1 C60-高分子混成材料之鑑定…………...………….…………..….74
4-1.1 PS76-Br與C60形成之C60-高分子混成材料之鑑定...……………74
4-1.1.1 PS76-C60之鑑定…………………………………………..……74
4-1.1.2 PS76-C60-PS115之鑑定…………………………………..…..…77
4-1.1.3 PS76-C60-PS115-C60之鑑定…………………….………..…..…80
4-1.2 Br-PS251-Br與C60形成之C60-高分子混成材料之鑑定…….…83
4-1.2.1 C60-PS251-C60之鑑定………….……….………………..……83
4-1.2.2 PS18-C60-PS251-C60-PS18之鑑定………………………..……86
4-1.2.3 PS177-C60-PS251-C60-PS177之鑑定………………………..……89
4-1.2.4 C60-PS177-C60-PS251-C60-PS177-C60之鑑定……………….……92
4-2 C60-高分子混成材料之性質探討…………...………….…………..….95
4-2.1 PS76-Br與C60形成之C60-高分子混成材料之性質探討...………95
4-2.2 Br-PS251-Br與C60形成之C60-高分子混成材料之性質探討.…100
4-3 C60-高分子混成材料之熱分析..…….………...………….…………...105
4-3.1 PS76-Br與C60形成之C60-高分子混成材料之熱分析…….……105
4-3.2 Br-PS251-Br與C60形成之C60-高分子混成材料之熱分析…..…107
4-4 C60-高分子混成材料之自組裝行為探討….……….…………..………110
4-4.1 PS76-Br與C60形成之C60-高分子混成材料之自組裝行為……110
4-4.2 Br-PS251-Br與C60形成之C60-高分子混成材料之自組裝行為..115

第五章 結論…………………..……………………………………………....120

第六章 參考文獻………………….………..………….…..………...……….121

圖目錄

頁數
圖1.1 由20個六角形及12個五角形所組成的C60模型..……...... 1
圖1.2 C60之製備方法總覽…………………………….………… 5
圖1.3 C60、C70與鄰二甲苯的三元固液態相圖及工業生產流程.... 6
圖1.4 原子轉移自由基加成反應示意圖……………...………... 9
圖1.5 金屬觸媒轉移ATRP聚合反應……………..…...……….. 10
圖1.6 The scheme representing functional polymers prepared by ATRP…………………………………………………….... 11
圖2.1 C60-styrene copolymers之反應式………………………… 13
圖2.2 以PS-N3與C60反應合成PS-C60之反應式……………… 14
圖2.3 Synthesis Procedure of Monosubstituted C60 Derivatives of PAA………………………………………………………… 14
圖2.4 TEM images of PAA-C60 film cast from water solution…… 15
圖2.5 Schematic presentation of the three step synthesis of PPO-bonded C60……………………………………………
15
圖2.6 Synthetic Route of C60-DMAEMA60-b-EO105-b- DMAEMA60-C60……………………………………………
16
圖2.7 TEM micrograph obtained from 0.84 mg ml-1 aqueous solution of Ⅳ…………………………………………….... 17
圖2.8 AFM micrograph obtained from 0.84 mg ml-1 aqueous solution of Ⅳ………………………..………………………
17
圖2.9 Synthesis Scheme of C60-PAA……………………….…… 18
圖2.10 Micrographs demonstrating the morphology change of unneutralized PAA85-b-C60 (samples prepared from a 5mM polymer solution) induced by the binding of TX100:(a) CTX100=0 mM, (b) CTX100=1 mM, (c) CTX100=1.7 mM, and (d) CTX100=2mM……………………………….….…………



18
圖2.11 Micrographs demonstrating the morphologies of the PAA-b -C60/TX100 mixture (samples prepared in a solution of 5mM PAA-b-C60 mixed with 0.7mMTX100) at different α values.(a)0, (b) 0.05,(c) 0.1, and (d) 0.15…………………... 19
圖2.12 Synthesis Schemes of PAA-C60 and C60-PAA-C60…………. 20
圖2.13 TEM images of PAA-C60 aggregates (sample preparedfrom 0.1 wt % aqueous solution) at (a)α=0 and (b)α=1……… 20
圖2.14 TEM images of C60-PAA-C60. aggregates (sample prepared from 0.1 wt % aqueous solution) at (a)α=0 and (b)α=1…..
21
圖2.15 The synthetic route of [C60-DMAEMAn-C(CH3)2COO -CH2]2……………………………………………..…………
22
圖2.16 Proposed micellar structures of IV in unbuffered distilled water and at pH=3………………………………………….
22
圖2.17 Reaction schemes employed for the preparation of well-defined amphiphilic block copolymer incorporated with a single C60 moiety at the diblock junction point, PEO45(-C60)-b-PS380……………………….....……………..
23
圖2.18 Typical TEM (a, b) and SEM (c) images of fullerene-containing hybrid vesicles self-assembled from PEO45(-C60)-b-PS380 in aqueous solution using 1,4-dioxane as the cosolvent……………………………………………...
24
圖2.19 Typical HRTEM images of fullerene-containing hybrid vesicles self-assembled from PEO45(-C60)-b-PS380 in aqueous solution using 1,4-dioxane as the cosolvent……….

24
圖2.20 Overall Scheme for Synthesis of Pyrene-Poly(N- isopropyl -acryl-amide)-Fullerene(4).Conditions:(a)CuCl, Me6TREN, DMF/H2O, 20℃, 2 h; (b) NaN3, DMF, 70 °C, 48 h; (c) C60, 1,2-dichlorobenzene, 150℃, 48h………..……..……………


25
圖2.21 Diagrammatic Representation of the Induction of Fluoresc -ence Quenching under Temperature Change…………….... 26
圖2.22 The general synthetic route of PSC60-I and PSC60-II……..… 27
圖2.23 以第一種方式得到的C60為‘結’之網狀高分子………...…. 28
圖2.24 The synthetic route of networks with C60 knots…………...... 28
圖2.25 以第二種方式得到的C60為‘結’之網狀高分子……………. 28
圖2.26 Synthesis of networks with C60 knots based on ‘living’ poly -styrene stars………………………………………………...
29
圖2.27 Synthetic Route of PMMA-C60…………………………… 29
圖2.28 Tapping mode AFM height images of isolated PMMA-C60 spin-cast from a dilute solution in chloroform on mica. The height profile measured along the white line in the image is also shown………………………………………………….
30
圖2.29 Synthesis of it- and st-PMMA-C60………………….………. 30
圖2.30 SEM (a, c, d, e) and TEM (b, f) images of it-35-C60 (a, b),st-53- C60 (c), it-229- C60 (d), and st-360- C60 (e, f) cast from solutions in H2O/CH3CN (1/9, v/v) on mica (a, c-e) or TEM grid precoated with poly-(vinyl formal) (b, f). The solutions were allowed to stand at room temperature for 96 hr. before measurements. The TEM images were taken with -out staining and the black areas indicate C60-rich regions.....





31
圖2.31 SEM images of stereocomplexes between it-35 and st-54 (a),it-35-C60 and st-53- C60 (b), and it-229- C60 and st-360- C60 (c) cast from H2O/CH3CN (1/9, v/v) solutions on mica after immediately mixing each sample solution (it/st ) 1/2); the polymer concentration was 0.2 mg/mL…………….…...
32
圖2.32 SEM images of stereocomplexes between it-35-C60 (aggreg -ate) and st-53- C60 (aggregate) (a), it-229- C60 (aggregate) and st-360- C60 (aggregate) (b) cast from H2O/CH3CN (1/9, v/v) solutions (it/st=1/2) on mica; the polymer concentra -tion was 0.2 mg/mL. Magnified SEM images correspond -ing to the area indicated by dotted squares in (a) and (b) are also shown together with schematic representations of the nanonetworks………………………………………………






32
圖2.33 Schematic representation of the formations of core-shell nanospheres and nanonetworks based on it- and st-PMMA -C60’s through their stereocomplex formation combined with self-assembly of the terminal C60……………..………..
33
圖2.34 Grafting of poly(N-vinylcarbazolyl)lithium with tertbutyl -lithium onto fullerene-C60.…………………………………
34
圖2.35 Scheme of the synthetic route used to prepare the 6-arm star-block copolymers with a C60 core…..…………………..
35
圖2.36 a) SAXS trace of a bulk sample of ST6-25-25. The inset corresponds to the TEM BF image showing the lamellar morphology. OsO4-stained PI lamellae appear dark grey.b) Schematic illustration of the organization of the block copolymer stars in a lamellar morphology. The PI domains are represented in red, PS domains in blue and the C60 as black spheres. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)……………………………………… 36
圖2.37 a) SAXS trace of a bulk sample of ST6-11-34. The inset corresponds to the TEM BF image showing the hexagonal packing of PS cylinders in a PI matrix. b) Schematic illustration of the organization of the block copolymer stars in a PS cylinder morphology. The PI domains are represented in red, PS domains in blue and the C60 as black spheres. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)…………………………………………………







37
圖2.38
a) SAXS trace of a bulk sample of ST6-56-14. The inset corresponds to the TEM BF image showing the hexagonal packing of PI cylinders in a PS matrix. b) Schematic illustration of the organization of the block copolymer stars in a PI cylinder morphology. The PI domains are represented in red, PS domains in blue and the C60 as black spheres. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)…………………………………………………. 38
圖2.39 a–c) Various TEM projections performed on cryo-microtomed sections of ST6-12-21. 50 nm-thick sections were cut at T=-80 ℃, coated with an amorphous carbon film and finally stained in vapors of OsO4 so that PI appears in black. The insets correspond to the FFT (bottom left corners) and simulations (top left corner) using TEMSim software. d) Schematic drawing showing a strut of the PS network of the gyroid structure containing the C60s. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)……………………………………………………… 39
圖2.40 C60 polymer之反應式……………………..……………….. 40
圖2.41 methanofullerene…………………………………………… 41
圖2.42 Bingel reaction mechanism: E is strong electron withdraw -ing group, L is leaving group……………………………....

41
圖2.43 The synthetic procedures for C60-anchored two-armed poly -(tert-butyl acrylate) 5 and model compound 6………….….
42
圖2.44 Synthesis of short-chain fullerene amphiphiles 2a-c and 3.... 43
圖2.45 TEM images of rod-like aggregates formed by amphiphilic fullerene derivatives 2b (upper-left and upper-right), 2a (lower-left), 2c (lower-right)……………………….……….. 43
圖2.46 SEM images of fullerene aggregates containing molecules 3 (left) and 2b (right) deposited on silicon substrate by spin coating…………………….…………………………………

43
圖2.47 TP-AFM (right) and cross section profiles (left) of the aggre -gates containing fullerene derivative (a) 2b (average verti -cal profile:50nm) and (b)3(average vertical profile: 43 nm) deposited by spin-coating on silicon surfaces……...………..

44
圖2.48 The synthetic routes for the novel monomers containing monosubstituted acetylene………………………………..… 45
圖2.49 The acetylene-containing monomers were copolymerized in hydrous CHCl3 at 30℃ for 24 h…………………….…….. 45
圖2.50 Synthetic Routes for the Preparation of Alkynyl-C60 Precursor…………………...…………………….…………. 46
圖2.51 Synthetic Routes Employed for the Preparation of (a) C60- PNIPAM98, (b) (C60)2-PNIPAM100, and (c) PEG113(-C60)-b- PNIPAM70………………………….…………………….…. 47
圖2.52 Typical TEM images obtained by drying 0.5 g/L aqueous solutions of (a) C60-PNIPAM98 and (b) (C60)2-PNIPAM100… 47
圖2.53 Synthetic Schemes of the PS-C60-Br and PMMA-C60-Br…... 48
圖2.54 由螢光光譜儀之結果推測PS-C60-Br於溶液中之可能構型……………………………………………………………
49
圖2.55 Synthetic Scheme of the [60]Fullerene-Containing PtBMA.. 50
圖2.56 Typical TEM micrographs: (a) 0.5 wt % FBMA in 0.75 EA molar composition, (b) 1.0 wt % FBMA in 0.92 EA molar composition, (c) close-up view of a single aggregate of 0.5 wt % FBMA in 0.75 EA molar composition,and (d) close -up view of a single aggregate of 1.0 wt % FBMA in 0.92 EA molar composition………………..…………………….. 50
圖2.57 Pictorial representation of a [60]fullerene-containing PtBMA LCV. Top section has been cut off for clarity……... 51
圖2.58 Synthesis Scheme of PMAA-b-C60……………………….… 51
圖2.59 TEM images of PMAA-b-C60 at different degrees of neutralization and different concentrations of NaCl.(a)Charg -ed LCM aggregates atα=1 and(b)fractal pattern formed with the addition of NaCl,(c) fractal pattern becomes denser with further addition of NaCl.(d)LCM aggregates atα= 0, (e) salt crystallizes on the LCM, and (f) the crystallization of salt becomes denser……………………………………… 53
圖2.60 Synthetic Scheme for P(MAA102-b-DMAEMA67)-b-C60.... 53
圖2.61 TEM images of P(MAA102-b-DMAEMA67)-b- C60 aggre -gates formed in aqueous solution at pH 3 (a) and pH 11 (b)
54
圖2.62 Schematic representation of the possible microstructures of P(MAA102-b-DMAEMA67)-b-C60 in aqueous solutions at different pH values and temperatures. The inset is the enlar -gement of the CT complex………………………………… 54
圖2.63 Synthesis scheme of PMMA-b-C60 using ATRP………..… 55
圖2.64 TEM image of PMMA-b-C60 aggregates in solvent mix -tures: (a) zoom-in TEM image in 100 wt% EA, and (b) in 70 wt% EA………………………………………………… 55
圖2.65 Synthesis Scheme of Bet-PDMAEMA-b-C60.....................… 56
圖2.66 TEM micrographs of 0.2 wt % Bet-PDMAEMA-b-C60 in aqueous solution (a) in absence of salt (above UCST) and (b) in the presence of 0.5 M NaCl………………………… 57
圖2.67 C60Cln作為起始劑合成C60-PVK之反應式……………...... 58
圖2.68 C60-PSts及C60-PMMAs之反應式………………………... 58
圖2.69 Particle size distributions and micrographs demonstrating the morphology change of un-ionzied PAA85-b-C60 induced by the binding of TX100:(a) CTX100=0 mM;(b) CTX100=1 mM;(c) CTX100=1.7 mM;(d) CTX100=2 mM………………


59
圖2.70 Particle size distributions and micrographs demonstrating the morphology change of un-ionized di-end-capped C60-b -PAA83-b-C60 induced by the binding of TX100:(a) CTX100=0 mM;(b) CTX100=0.7 mM;(c) CTX100=1.7 mM;(d) CTX100=3.5 mM…………………………………………….. 60
圖2.71 Synthesis of Amphiphilic Polystyrene-b-Poly(N-isopropyl -acrylamide) (PS-b-PNIPAAm) and PS-C60-PNIPAAm Hybrid Materials……………………….…………………… 61
圖2.72 SEM images of (a) PS-C60, (b) PS-b-PNIPAAm, and (c) PS-C60- PNIPAAm morphologies from their solutions in chloroform (1 mg/mL) spin-coating on silicon surface. (d) AFM image of PS-C60-PNIPAAm toroids. The heights of the rings are about 37.5 nm……………………….………… 61
圖2.73 TEM images of PS-C60-PNIPAAm in chloroform solutions at concentra -tions of (a) 0.1 mg/mL, (b) 0.5 mg/mL, (c) 1.0 mg/mL, (d) 1.0 mg/mL in high amplification, (e) 1.5mg/mL, and (f) 2.0 mg/mL................................................


62
圖2.74 TEM images of PS-C60-PNIPAAm in (a) chlorobenzene and (b) chloroform/methanol (v/v:1/1) solutions of 1mg/mL 62
圖3.1 PS76-Br之反應流程圖............................................................ 65
圖3.2 Br-PS251-Br之反應流程圖……….................……………… 66
圖3.3 PS76-C60之反應流程圖……...………………….…………... 67
圖3.4 PS76-C60-PS115之反應流程圖………………………..…… 68
圖3.5 PS76-C60-PS115-C60之反應流程圖……………...................... 69
圖3.6 C60-PS251-C60之反應流程圖……………………………….. 70
圖3.7 PS18-C60-PS251-C60-PS18之反應流程圖…………………… 71
圖3.8 PS177-C60-PS251-C60-PS177之反應流程圖………………… 72
圖3.9 C60-PS177-C60-PS251-C60-PS177-C60之反應流程圖………… 73
圖4.1 PS76-C60¬之GPC圖………………………………………… 75
圖4.2 PS76-C60¬之FTIR光譜圖……………………………………. 75
圖4.3 PS76-C60¬之FTIR放大圖…………………………………… 76
圖4.4 PS76-C60¬之UV-vis光譜圖,樣品濃度為0.05mg/ml……… 76
圖4.5 PS76-C60-PS115之GPC圖…………………………………. 78
圖4.6 PS76-C60-PS115¬之FTIR光譜圖…………………………… 78
圖4.7 PS76-C60-PS115之FTIR放大圖……………………………... 79
圖4.8 PS76-C60-PS115¬之UV-vis光譜圖,樣品濃度為0.05mg/ml…. 79
圖4.9 PS76-C60-PS115-C60之GPC圖……………………………… 81
圖4.10 PS76-C60-PS115-C60¬之FTIR光譜圖………………………… 81
圖4.11 PS76-C60-PS115-C60¬之FTIR放大圖………………………… 82
圖4.12
PS76-C60-PS115-C60之UV-vis光譜圖,樣品濃度為0.05mg/ml………………………………………………… 82
圖4.13 C60-PS251-C60之GPC圖…………………………………….. 84
圖4.14 C60-PS251-C60¬之FTIR光譜圖……………………………… 84
圖4.15 C60-PS251-C60¬之FTIR放大圖……………………………… 85
圖4.16 C60-PS251-C60之UV-vis光譜圖,樣品濃度為1mg/ml…… 85
圖4.17 PS18-C60-PS251-C60-PS18之GPC圖………………………… 87
圖4.18 PS18-C60-PS251-C60-PS18¬之FTIR光譜圖…………………… 87
圖4.19 PS18-C60-PS251-C60-PS18之FTIR放大圖…………………… 88
圖4.20
PS18-C60-PS251-C60-PS18¬之UV-vis光譜圖,樣品濃度為1mg/ml……………………………………………………… 88
圖4.21 PS177-C60-PS251-C60-PS177之GPC圖………………………... 90
圖4.22 PS177-C60-PS251-C60-PS177之FTIR光譜圖………………… 90
圖4.23 PS177-C60-PS251-C60-PS177之FTIR放大圖………………….. 91
圖4.24
PS177-C60-PS251-C60-PS177之UV-vis光譜圖,樣品濃度為1mg/ml……………………………………………………… 91
圖4.25 C60-PS177-C60-PS251-C60-PS177-C60之GPC圖……………… 93
圖4.26 C60-PS177-C60-PS251-C60-PS177-C60¬之FTIR光譜圖………… 93
圖4.27 C60-PS177-C60-PS251-C60-PS177-C60¬之FTIR放大圖………… 94
圖4.28
C60-PS177-C60-PS251-C60-PS177-C60之UV-vis光譜圖,樣品濃度為0.05mg/ml………………………………………… 94
圖4.29
PS76-Br與C60形成之Polystyrene-C60混成材料之反應流程圖………………………………………………………. 95
圖4.30 PS76-Br與C60形成之Polystyrene-C60混成材料之GPC圖………………………………………………………........ 97
圖4.31 PS76-Br與C60形成之Polystyrene-C60混成材料之FTIR圖.. 98
圖4.32 PS76-Br與C60形成之Polystyrene-C60混成材料於480cm-1至610cm-1區域之FTIR放大圖……………………….…... 99
圖4.33 Br-PS251-Br與C60形成之Polystyrene-C60混成材料之反應流程圖……………………………………………....……… 100
圖4.34 Br-PS251-Br與C60形成之Polystyrene-C60混成材料之GPC圖…………………………………………………………… 102
圖4.35 Br-PS251-Br與C60形成之Polystyrene-C60混成材料之FTIR圖…………………………………………………………… 103
圖4.36 Br-PS251-Br與C60形成之Polystyrene-C60混成材料於480cm-1至610cm-1區域之FTIR放大圖……….….....…... 104
圖4.37 PS76-Br與C60形成之Polystyrene-C60混成材料之TGA圖.. 105
圖4.38 PS76-Br與C60形成之Polystyrene-C60混成材料之TGA微分圖………………………………………………………… 106
圖4.39 Br-PS251-Br與C60形成之Polystyrene-C60混成材料之TGA圖…………………………………………………………… 108
圖4.40 Br-PS251-Br與C60形成之Polystyrene-C60混成材料之TGA微分圖……………………………………………………… 108
圖4.41 PS76-Br與C60形成之Polystyrene-C60混成材料溶於氯仿中之SEM圖……………………………………………… 111
圖4.42 PS76-Br與C60形成之Polystyrene-C60混成材料溶於氯仿中之TEM圖…………………………………………… 112
圖4.43 PS76-Br與C60形成之Polystyrene-C60混成材料溶於氯仿/甲醇中之SEM圖…………………………………………. 113
圖4.44 PS76-Br與C60形成之Polystyrene-C60混成材料溶於氯仿/甲醇混合溶液中之TEM圖………………………………... 114
圖4.45 Br-PS251-Br與C60形成之Polystyrene-C60混成材料溶於氯仿中之SEM圖…………………………………………… 116
圖4.46 Br-PS251-Br與C60形成之Polystyrene-C60混成材料溶於氯仿中之TEM圖……….......……...…….…….…………....... 117
圖4.47 Br-PS251-Br與C60形成之Polystyrene-C60混成材料溶於氯仿/甲醇混合溶液中之SEM圖…….……….…..….…….. 118
圖4.48 Br-PS251-Br與C60形成之Polystyrene-C60混成材料溶於氯仿/甲醇混合溶液中之TEM圖………………………...….
119



表目錄

頁數
表1.1 C60之物理性質與化學性質…………………………………… 3
表1.2 C60之溶解度…………………………………………………. 4
表3.1 實驗藥品…………………………..……………………...…..... 63
表4.1 PS76-Br與C60形成之Polystyrene-C60混成材料之分子量及PDI值表…..……..……..……..……..…..……..……..……...….… 96
表4.2 Br-PS251-Br與C60形成之Polystyrene-C60混成材料之分子量及PDI值表.....……………………………………………............. 102
表4.3 PPS76-Br與C60形成之Polystyrene-C60混成材料之裂解溫度表…………………………………………………………..…… 106
表4.4 Br-PS251-Br與C60形成之Polystyrene-C60混成材料之裂解溫度表………………………………………………………………. 109


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