雙團聯共聚物之合成與層狀黏土複合材料之製備及其吸持特性之研究

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何如珍(Ru-Zhen He) 查詢紙本館藏

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論文名稱

雙團聯共聚物之合成與層狀黏土複合材料之製備及其吸持特性之研究
(Layered clay-composite materials with diblock copolymer for enhanced sorption capacity)

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摘要(中)

近年來，聚合物奈米材料之相關研究蓬勃發展，其中以團聯聚合物(Block copolymer)之研究最受到矚目，研發成果已廣泛被應用於橡膠界面工業、生物相關及光電等產業領域。因此，本研究重點在於自行合成雙團聯共聚物(Diblock copolymer)及選用市售團聯共聚物，分別嵌入層狀黏土之層隙間，形成黏土複合材料，並針對嵌入共聚物進行特性鑑定，經製備完成之團聯共聚物黏土複合材料，再進行對非離子有機污染物(NOCs)及無機重金屬吸持特性作探討。
本研究自行合成M-D及M-A雙團聯聚合物，經由NMR及GPC鑑定確定RAFT聚合法成功合成雙團聯共聚物，並能有效控制分子量分佈(Polymerdispersity index，PDI)。另外與市售雙團聯聚合物分別嵌入層狀黏土所製備之雙團聯共聚物改質黏土，經由特性分析發現，團聯共聚物已成功植入層狀矽酸鹽中，使層隙間距增加且未造成剝離，而有機碳含量也明顯增高，FTIR分析結果亦證實改質黏土表面存在羧基、胺基等官能基。根據重金屬吸附實驗得知帶有羧基之團聯共聚物改質黏土，隨著pH值上升其所帶的負電荷越多，與重金屬的親和力會越高，而在最高pH值時，有最佳的吸附效果。另外，由陰離子污染物吸附實驗可得知帶有胺基之改質黏土，在酸性環境下帶正電，並證明在低pH值時，對陰離子污染物有最佳的親和力。此外，因團聯共聚物之M鏈段具有強疏水性，可大大增加改質黏土的有機碳含量，土壤經改質後對有機污染物之分佈效果明顯較文獻結果佳。本研究製備之團聯共聚物改質黏土經研究結果顯示，確實可達成同時對非離子(BTEX)、陽離子(Pb2+、Zn2+)及陰離子(Cr2O72-)污染物兼具高吸持能力之黏土複合材料。

摘要(英)

In recent years various polymer and nanomaterias have been developed. Among those, block polymers and copolymers are the most concerned for scientists due to their unique natures. Current researches have been widely applied on different areas including rubbers, biomaterials and optoelectronic and semiconductors. Therefore, this research aims at polymerization of diblock copolymer, and clay-composite materials in which polymers are intercalated into interlayer of clay. These clay-composite materials were characterized and confirmed by various analytical techniques. Such clay-composite materials are considered to greatly enhance the distribution of NOCs (Nonionic Organic Compounds), and also to increase the affinity for inorganic pollutants.
The polymerization of diblock copolymer, M-D and M-A, were successfully synthesized by RAFT polymerization method and were confirmed by nuclear magnetic resonance (NMR) spectral analysis. The RAFT polymerization was capable of controling molecular weight distribution effectively which further more confirmed by Gel Permeation Chromatography (GPC) analysis. SAXS X-ray diffraction (XRD) and transmission electron microscope (TEM) were used for studying intercalated materials in the silicate. The results showed that diblock copolymers are intercalated into interlayer of clay, and maintain the structure of silicate layer. Organic carbon content by wet oxidation method indicated this successful modification. As depicted in the FT-IR spectrum, the clay composite materials displayed specific functional group of diblock copolymer. The results showed that adsorption capacity increased with increasing pH value. The dimethylaminoethyl methacrylate can be protonated (positively charged) function as anionic pollutants adsorbent. The results also provided the affinity of modified clay for Cr2O72- is increased owing to the occurrence of negative zeta potential. Thus, clay-composite material can possesses both positive and negative charges and thus can act as dual sorbents for both cationic and anionic pollutants. Sorption of BTEX by modified soil indicated that distribution coefficient of BTEX is inversely proportional to their water solubility. The diblock copolymer modifiers improved the distribution ability of nonionic organic compounds was also shown in this study.

關鍵字(中)

★ 團聯共聚物
★ 改質黏土
★ BTEX
★ RAFT聚合法
★ Cr2O72-

關鍵字(英)

★ Diblock copolymer
★ Interlayer
★ Modification
★ BTEX
★ RAFT polymerization
★ Clay-composite material
★ Cr2O72-

論文目次

目次頁次
目錄 I
圖目錄 IV
表目錄 VIII
第一章前言 1
1-1 研究緣起 1
1-2 研究目的與內容 3
第二章文獻回顧 4
2-1 團聯共聚物及其理化特性 4
2-1-1 何謂團聯共聚物 4
2-1-2 團聯共聚物的微胞化行為 6
2-1-3 pH對團聯共聚物的影響 7
2-2 團聯共聚物之合成和應用 8
2-2-1 團聯共聚物之合成 8
2-3 層狀黏土之分散與有機化合物修飾 13
2-3-1 層狀矽酸鹽結構 13
2-3-2 層狀黏土之分散型態 14
2-3-3 層狀黏土之有機化合物修飾 16
2-4 共聚物於層狀黏土層隙間之反應機制與製備 17
2-4-1 共聚物與黏土間的作用力及反應機制 17
2-4-2 高分子/層狀黏土複合材料之製備 18
2-5 土壤對污染物之吸持作用 (sorption) 20
2-5-1 吸附理論 (adsorption) 20
2-5-2 分佈理論 (partitioning) 21
2-5-3 等溫吸附模式 24
2-5-4 等溫吸附曲線 26
第三章研究方法 29
3-1 研究內容與流程 29
3-2 實驗設備 31
3-3 實驗材料 34
3-3-1 不含有機質土壤 34
3-3-2 有機改質劑 35
3-3-3 團聯共聚物單體之選擇 35
3-3-4 非離子性有機污染物 37
3-3-5 重金屬標準品 38
3-3-6 溶劑 38
3-4 實驗方法 39
3-4-1 團聯共聚物合成實驗 39
3-4-2 高分子/層狀矽酸鹽複合土壤之製備 42
3-4-3 高分子/層狀矽酸鹽複合材料對污染物之吸持實驗 43
第四章結果與討論 46
4-1 預聚合團聯共聚物之特性分析 46
4-1-1 團聯共聚物之GPC分子量分析 46
4-1-2 團聯共聚物之NMR結構鑑定 49
4-2 改質黏土之物化特性分析 53
4-2-1 小角度X光繞射分析( SAXS ) 54
4-2-2 穿透式電子顯微鏡( TEM ) 59
4-2-3 比表面積、平均孔徑與孔徑分佈 63
4-2-4 有機碳含量測定 67
4-2-5 紅外線光譜( FTIR ) 68
4-3 團聯共聚物改質黏土對金屬之吸附 73
4-3-1 帶有羧基之改質黏土對吸附之影響 73
4-3-2 帶胺基之改質黏土對重金屬之吸附 81
4-4 團聯共聚物改質黏土對有機污染物之吸持作用 87
4-4-1 不同有機污染物(BTEX)之吸持行為 88
4-4-2 不同改質黏土對BTEX吸持之影響 92
4-4-3 改質黏土對BETX分佈常數之影響 95
4-5 改質土壤對無機陰離子之吸附作用 100
4-5-1 帶有胺基之改質黏土對吸附實驗之影響 100
第五章結論與建議 105
5-1 結論 105
5-2 建議 106
參考文獻 108

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指導教授

李俊福(Jiunn-Fwu Lee)

審核日期

2017-7-25

推文