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研究生: 郭景隆
Guo, Jing-Long
論文名稱: 兩性共聚物:合成以及對水泥砂漿中氧化石墨烯分散性之影響
Amphoteric Copolymer: Synthesis and Its Effect on the Dispersibility of Graphene Oxide in Mortars
指導教授: 許貫中
Hsu, Kung-Chung
呂家榮
Lu, Chia-Jung
口試委員: 許貫中
Hsu, Kung-Chung
呂家榮
Lu, Chia-Jung
黃中和
Huang, Chung-Ho
王曄
Wang, Yeh
口試日期: 2022/09/19
學位類別: 碩士
Master
系所名稱: 化學系
Department of Chemistry
論文出版年: 2022
畢業學年度: 110
語文別: 中文
論文頁數: 93
中文關鍵詞: 兩性共聚物合成氧化石墨烯分散水泥砂漿抗壓強度
英文關鍵詞: amphoteric copolymer, synthesis, graphene oxide, dispersion, cement mortar, compressive strength
研究方法: 實驗設計法比較研究觀察研究文件分析法現象分析內容分析法
DOI URL: http://doi.org/10.6345/NTNU202201549
論文種類: 學術論文
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  • 本篇論文的研究主要為合成出一種羧酸系兩性離子型共聚物PD (單(5-氨基-2-(1-(2-((羧甲基)二甲基氨基)乙氧基)-1-氧代丙烷-2-基)-4-甲基-5-氧代戊酸酯)二鈉),用來改善氧化石墨烯在水泥砂漿中的分散,提升試體的抗壓強度。實驗過程中使用馬來酸酐和DMEA(N,N-二甲基乙醇胺)合成DME(二甲基胺乙基氧羰基丙烯酸),然後再與氯丁酸鈉鹽反應得到單體DCA(N,N-二甲基((羧酸)丙烯醯氧基乙基)乙酸鈉),最後使用過硫酸銨為起始劑,與不同比例的丙烯醯胺(AM)經由自由基聚合反應合成得到共聚物PD,經由FTIR和1H-NMR光譜鑑定共聚物的分子結構,並以GPC/SEC測得其分子量。另外,使用modified Hummers法將石墨烯氧化成氧化石墨烯(GO)。
    將PD加入含GOA的人工孔隙溶液中,透過沉降體積試驗、黏度實驗、粒徑分布與界達電位的測試,探討PD對於GO在人工孔隙溶液中的分散效果。測試結果顯示, GO在人工孔隙溶液中的沉降時間隨著PD之AM/DCA比例的增加,呈現先增後減的趨勢。其中PD在AM/DCA=5時有最長的沉降時間;此外,GO在溶液中的沉降時間隨著PD分子量的上升或添加量的增加,呈現先增後減之趨勢。其中以添加10wt% PD15b時,GO在溶液中的沉降時間為最長,達到45小時,此時溶液的黏度為最低(3.08 mPa‧s),溶液中GO的D50粒徑為最小、界達電位之負值為最大,分別為127 nm和-25.5 mV,亦即在所合成的共聚物中以PD15b(AM/DCA=5, M̅n=1.8×104)對於氧化石墨烯在孔隙溶液中有最好的分散效果。將PD15b加入含GOA的水泥砂漿中,進行抗壓強度測試,發現添加10wt% PD15b與0.05wt% GOA的砂漿試體,在28天的抗壓強度為34.6 MPa,與未添加GOA、共聚物的控制組相比提升了52.4%。

    This thesis is to synthesize a zwitterionic carboxylate copolymer PD(mono(5-amino-2-(1-(2-((carboxylatomethyl)dimethylammonio)ethoxy)-1-oxopropan-2-yl)-4-methyl-5-oxopentanoate)) as a dispersant to improve the dispersion of graphene oxide(GO)in cement mortars and to promote the compressive strength of the cement-based materials.
    Experimentally, maleic anhydride and DMEA(N,N-dimethylethanolamine) was used to synthesize DME(3-((2-(dimethylamino)ethoxy)carbonyl)acrylic acid).
    Then, DME was reacted with 4-chlorobutyrate to obtain the monomer DCA (N,N-dimethyl(3-β-(carboxylate) acryloyl oxyethyl) ethanoate). Thereafter, PD copolymer was prepared from DCA 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 PD, and GPC/SEC was used to determine the molecule weight of the prepared polymer. Besides, GOA was prepared from graphene using the modified Hummers method.The dispersion property of GOA in the artificial pore solution with PD was evaluated through the sedimentation test, viscosity measurements, size distribution and zeta potential test. The results indicated the sedimentation time of GO in the artificial pore solution increased with AM/DCA ratio of polymer first, reached a maximum value at AM/DCA=5, and then decreased afterwards. The sedimentation time of GO in the pore solution also increased first,reached a maximum value at M̅n=1.8×104, and then decreased afterwards. Namely, PD15b which has AM/DCA=5 and M̅n=1.8×104 showed the best performance.
    GO in the pore solution with 10 wt% PD15b was found to exhibit the longest sedimentation time, the lowest viscosity, the smallest particle size and highest absolute value of zeta potential of GO, which is 45 hours, 3.08 mPa·s, 127 nm, and -25.5 mV, respectively. Finally, the measured compressive strength of mortar with 0.05wt% GOA and 10wt% PD15b at 28days were 34.6MPa, which were 52.4% increased relative to the mortar without any dispersant or GOA present.

    第一章緒論1 1-1研究背景1 1-2研究動機3 1-3研究目的9 第二章文獻回顧10 2-1氧化石墨烯10 2-1-1氧化石墨烯之合成10 2-1-2氧化石墨烯之特性及應用13 2-2水泥15 2-2-1水泥的種類15 2-2-2卜特蘭水泥16 2-2-3卜特蘭水泥的水化反應18 2-3添加氧化石墨烯至水泥的效果及困境20 2-4高分子型分散劑25 2-4-1高分子型分散劑的作用及種類25 2-4-2PC強塑劑對於水泥基材料中GO的分散機制32 2-4-3靜電排斥效應33 2-4-4立體障礙效應35 第三章實驗方法36 3-1實驗流程36 3-2實驗材料與儀器38 3-2-1實驗材料38 3-2-2實驗儀器41 3-3 實驗方法42 3-3-1氧化石墨烯的製備42 3-3-2共聚物的合成43 3-4結構鑑定與分析46 3-4-1FT-IR光譜46 3-4-2NMR光譜分析47 3-4-3GPC/SEC測試48 3-5 共聚物對氧化石墨烯在溶液中之分散性測試50 3-5-1沉降實驗50 3-5-2黏度量測53 3-5-3粒徑分布量測56 3-5-4界達電位量測58 3-6 添加共聚物/氧化石墨烯之水泥砂漿性質分析60 3-6-1水泥砂漿之拌製60 3-6-2水泥砂漿之抗壓強度測試62 第四章實驗結果與討論63 4-1氧化石墨烯之IR光譜鑑定63 4-2共聚物之光譜分析64 4-2-1共聚物之IR光譜分析64 4-2-2共聚物之1H-NMR光譜分析66 4-3共聚物之分子量測定72 4-4共聚物對氧化石墨烯在溶液中沉降時間之影響75 4-5共聚物對含氧化石墨烯之人工孔隙溶液的黏度影響80 4-6共聚物對溶液中氧化石墨烯粒徑分布的影響81 4-7共聚物對溶液中氧化石墨烯界達電位的影響84 4-8氧化石墨烯與共聚物對水泥砂漿抗壓強度的影響86 第五章結論88 參考文獻90

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