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研究生: 許永
HSU, Yung
論文名稱: 羧酸型共聚物:合成與對於砂漿中氧化石墨烯分散性的影響
Carboxylate Dispersant: Synthesis and its Effects on the Dispersion of Graphene Oxide in Mortars
指導教授: 許貫中
Hsu, Kung-Chung
王禎翰
Wang, Jeng-Han
口試委員: 王曄 黃中和 許貫中 王禎翰
口試日期: 2021/09/30
學位類別: 碩士
Master
系所名稱: 化學系
Department of Chemistry
論文出版年: 2021
畢業學年度: 109
語文別: 中文
論文頁數: 87
中文關鍵詞: 羧酸系共聚物合成氧化石墨烯分散砂漿機械性質
英文關鍵詞: carboxylate copolymer, synthesis, graphene oxide, dispersion, mortar, mechanical property
DOI URL: http://doi.org/10.6345/NTNU202101650
論文種類: 學術論文
相關次數: 點閱:150下載:0
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  • 本篇研究目標是合成一種羧酸系兩性離子型共聚物PDA(聚(N,N,N-二甲基((羧酸)丙烯醯氧基乙基)丁酸鈉-丙烯醯胺),作為共聚物用來改善氧化石墨烯在水泥基材料的分散性以提升試體的機械性質。先使用馬來酸酐和N,N-二甲基胺乙醇合成DME(二甲基胺乙基氧羰基丙烯酸),再與4-氯丁酸反應得到單體DCB(N,N,N-二甲基((羧酸)丙烯醯氧基乙基)丁酸鈉),最後使用過硫酸銨(APS)為起始劑,與不同比例丙烯醯胺(AM)經由自由基聚合反應合成得到兩性離子型共聚物PDA,PDA經由FTIR和1H-NMR光譜鑑定其結構,以GPC測定其分子量。另外,使用Hummers法將石墨烯氧化成氧化石墨烯(GO)。
    將PDA加入含氧化石墨烯的水溶液中,透過沉降體積、粒徑分布、界達電位與黏度實驗測試,探討PDA對於水溶液中GO的分散效果。測試結果顯示,在人工孔隙溶液中共聚物對於GO的沉降時間隨著AM/DCB比例的增加呈現先增後減的趨勢,PDA在AM/DCB=4時有最長的沉降時間;另外,GO的沉降時間隨著PDA分子量的上升或添加量的增加而增長,因此PDA41添加量為20 wt%時,GO的沉降時間為最長達65小時,此時溶液的黏度為最低(2.88 mPa‧s),溶液中GO的D50粒徑為最小、負界達電位為最大,分別為287 nm和-28.2 mV。因此在所合成的共聚物中PDA41有最好的分散效果。將PDA41加入含氧化石墨烯的水泥砂漿中,測試砂漿試體的抗壓強度與抗彎強度。結果顯示,添加20 wt%的PDA41與0.05 wt%的GO的水泥砂漿試體,在28天的抗壓強度為34.7 MPa,抗彎強度為6.73 MPa,與未添加共聚物的控制組相比提升了57%與99%。

    This thesis is to synthesize a zwitterionic carboxylate copolymer PDA (Poly(N,N,N-dimethyl((carboxylate) acryloyloxyethyl) butyrate-co-acrylamide)) as a dispersant to improve the dispersion of graphene oxide (GO) in cement-based materials and the mechanical properties of mortar. First, maleic anhydride and N,N-dimethylaminoethanol was used to synthesize DME(3-((2-(dimethylamino)ethoxy)carbonyl)acrylic acid). Then, DME was reacted with sodium 4-chlorobutyric acid to obtain the monomer DCB(N,N,N-dimethyl((carboxylate) acryloyloxyethyl) butyrate). Thereafter, PDA copolymer was prepared from DCB and acrylamide(AM) through free radical polymerization by using ammonium persulphate as an initiator. FT-IR and 1H-NMR were used to identify the structure of PDA, and GPC was used to determine the molecule weight of the prepared polymer. Besides, graphene oxide was prepared from graphene using the Hummers method.
    The dispersion property of PDA was evaluated through the sedimentation test, size distribution, zeta potential and viscosity measurements. The results indicated the sedimentation time of GO in the artificial pore solution increased with AM/DCB ratio of polymer first, reached a maximum value at AM/DCB=4, and then decreased afterwards. Increase of the molecular weight of PDA or polymer dosage increased the sedimentation time of GO in the artificial pore solution. Apparently, PDA41 which has AM/DCB=4 and the highest molecular weight showed the best performance. GO in the pore solution with 20 wt% PDA41 was found to have the smallest particle size and highest absolute value of zeta potential of GO, and longest sedimentation time. Finally, the compressive and flexural strength of mortar with 0.05 wt% of graphene oxide and 20 wt% of PDA41 at 28days were 34.7 MPa and 6.73 MPa, which were 57% and 99% increased relative to the mortar without any dispersant or GO present.

    第一章 緒論 1 1-1 研究背景 1 1-2 研究動機 1 第二章 文獻回顧 3 2-1 石墨烯 3 2-2 氧化石墨烯 9 2-3 水泥 13 2-3-1 卜特蘭水泥 13 2-3-2 水泥的水化 13 2-3-3 氧化石墨烯對水泥的影響 16 2-4 添加氧化石墨烯至水泥漿的困境 20 2-5 高分子型分散劑 24 2-5-1 靜電排斥理論 25 2-5-2 立體障礙效應 28 第三章 實驗流程與方法 31 3-1 實驗流程 31 3-2 實驗藥品與儀器 33 3-2-1 藥品 33 3-2-2 實驗設備 35 3-3 實驗方法 36 3-3-1 氧化石墨烯的製備 36 3-3-2 共聚物PDA的合成 37 3-4 結構鑑定與分析 40 3-4-1 FT-IR光譜儀 40 3-4-2 1H-NMR光譜儀 40 3-4-3 凝膠滲透層析儀 41 3-5 分散劑對氧化石墨烯在孔隙溶液之分散性測試 42 3-5-1 沉降實驗 42 3-5-2 黏度量測 42 3-5-3 GO粒徑分布量測 42 3-5-4 GO界達電位量測 43 3-6 添加PDA與氧化石墨烯的水泥漿性質分析 44 3-6-1 水泥漿體之拌製 44 3-6-2 掃描式電子顯微鏡 45 3-7 添加PDA/GO的水泥砂漿性質分析 46 3-7-1 水泥砂漿之拌製 46 3-7-2 抗壓強度測試 48 3-7-3 抗彎強度測試 49 第四章 結果與討論 50 4-1 氧化石墨烯的結構鑑定 50 4-1-1 氧化石墨烯的IR光譜 50 4-1-2 氧化石墨烯的微觀結構 51 4-2 分散劑的光譜鑑定 53 4-2-1 分散劑的IR光譜分析 53 4-2-2 單體與分散劑的1H-NMR光譜分析 55 4-2-3 PDA的分子量測定 60 4-3 共聚物對GO沉降體積的影響 63 4-4 不同分散劑對氧化石墨烯粒徑分布的影響 67 4-5 不同分散劑對GO界達電位的影響 69 4-6 不同分散劑的黏度影響 70 4-7水泥漿的微觀結構分析 71 4-8 PDA與GO對砂漿抗壓強度的影響 77 4-9 PDA與GO對砂漿抗灣強度的影響 79 第五章 結論 81 參考文獻 82

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