臺灣博碩士論文加值系統

本研究以2,2,6,6-四甲基哌啶-1-氧基（2,2,6,6-Tetramethylpiperidine-1-oxyl；TEMPO）媒介氧化反應將羧基導入天然纖維表面，後續以均質機和超音波振盪機處理氧化後的纖維，製得纖維素奈米纖維（Cellulose nanofibers；CNF）。依據反應時的氧化系統的反應環境、氧化劑添加量、反應時間、緩衝溶液使用種類對製得CNF的性質有所不同。所製得之CNF進行羧基含量、聚合度、光透射率和保水值等性質評估。隨後以CNF作為造紙添加劑的應用評估，將不同的製備條件得到性質有所差異的CNF添加入紙漿中，選擇4種不同聚合度的CNF作為紙張性質的改良劑，探討所添加CNF不同聚合度對於紙張性質的影響，測試添加10％CNF後之手抄紙的密度、平滑度、透氣度、不透明度、光散射係數、抗張強度、破裂強度、撕裂強度和耐折強度等的影響。
以TEMPO法在鹼性環境（TEMPO/NaBr/NaClO）下製備CNF，當氧化劑添加量為0、1.5、3.0、5.0和6.0 mmol/g時，所得之CNF的羧基含量依序為0.16、0.79、1.07、1.30和1.42 mmol/g，聚合度為962、176、144、130和124。氧化劑添加量較高的樣品，其光透射率也會越高，氧化劑添加3 mmol/g以上的樣品，其光透射率皆可達80％或以上。在中性環境（TEMPO/ NaClO /NaClO2）下，反應時間從0-60 hr時，CNF的羧基量會從0.16增加至0.83 mmol/g，聚合度會從962降低至345。在相同反應時間下，氧化劑添加量會影響CNF的羧基量和聚合度，CNF的羧基量和聚合度隨著氧化劑的添加量增加而增加。中性環境製備的CNF，其光透射率則較低，但由於其氧化程度較低，即使在相同的機械處理下，尚有較多未被完全分散的部分。
以TEMPO氧化法製備的CNF以FTIR測定時在1600 cm-1位置皆有C=O的吸收峰，顯示CNF具有COONa的官能基。隨氧化程度之進行，羧基含量增加，1600 cm-1位置的吸收峰有增大的趨勢。
在紙漿中添加入10％不同聚合度的CNF分散液作為添加助劑，抄成紙張後測試紙張的性質。添加聚合度較低（DPv = 124）的CNF可以使紙張的密度增加5.5％、透氣抵抗增加（70→962）、光散射係數降低31.5％。添加聚合度較高（DPv = 540）的CNF可以使紙張的抗張強度、破裂強度和耐折強度分別增加28.4％、27.7％和59.4％。
推論CNF可以提升紙張性質的機制大致有四點：（1）CNF表面的羥基可以與纖維上的羥基產生氫鍵結合，增加纖維與纖維之間的結合面積和結合強度；（2）CNF奈米等級的尺寸可以在濾水過程中與纖維產生毛細管作用；（3）奈米尺寸的CNF容易填補於纖維與纖維之間的孔隙中，產生網狀構造；（4）長徑比越大的CNF具有更高的強度以增加補強強度。

In this study, 2,2,6,6-Tetramethylpiperidine-1-oxyl (TEMPO) was used to introduce carboxyl groups into the natural fiber surface, and obtained cellulose nanofibers (CNF) by treating the oxidized fibers with a homogenizer and an ultrasonicator. The reaction environment, amount of oxidant added, reaction time and the type of buffer solution of the oxidation system will have effect on the properties of CNF. Determine the carboxyl groups content, polymerization degree, light transmittance and water retention value of CNF. The use of CNF as a papermaking additive was subsequently evaluated. 10％CNF was added into the pulp with different preparation conditions. Four kinds of CNFs with different degrees of polymerization were selected as the improvers of paper properties. The effects of the degree of polymerization of CNF on the properties of paper were investigated. The density, smoothness, air permeability, opacity, light scattering coefficient, tensile strength, burst strength, tear strength and folding strength of the paper were measured.
In the alkaline environment (TEMPO/NaBr/NaClO), When the amount of oxidant added was 0, 1.5, 3.0, 5.0 and 6.0 mmol / g, the carboxyl content of CNF was 0.16, 0.79, 1.07, 1.30 and 1.42 mmol / g, the degree of polymerization was 962, 176, 144, 130 and 124. The more oxidant addition, the higher the light transmittance of the sample. The oxidant added 3 mmol/g above the sample of its light transmittance are more than 80％. In the neutral environment（TEMPO/ NaClO /NaClO2）, CNF prepared by TEMPO oxidation will be affected by the reaction time and the addition of oxidant. When the reaction time ranged from 0 to 60 hr, the amount of carboxyl group of CNF increased from 0.16 to 0.83 mmol/g, and the degree of polymerization decreased from 962 to 345. The amount of carboxyl group and the degree of polymerization of CNF were affected by the addition of oxidant at the same reaction time. The amount of carboxyl group and the degree of polymerization of CNF increased with the addition of oxidant. CNF prepared by neutral environment has a low light transmittance, and because of its low degree of oxidation. Even under the same mechanical treatment, there are many parts that are not completely dispersed.
CNF prepared by TEMPO oxidation method has an absorption peak of C=O at 1600 cm-1 when measured by FTIR, showing that CNF has COONa functional groups. With the increase of oxidation degree, the content of carboxyl group increased, and the absorption peak at 1600 cm-1 increased.
10% different degree of polymerization of CNF dispersion was added to the pulp as an additive and then test the property of the paper. The addition of a CNF with a low degree of polymerization (DPv = 124) increases the density of the paper by 5.5%, the increase in air resistance (70 → 962), and the light scattering coefficient by 31.5%. The addition of CNF with high polymerization degree (DPv = 540) can increase the tensile strength, breaking strength and folding strength of the paper by 28.4%, 27.7% and 59.4%, respectively.
There are four points that the mechanism of improvement of properties of paper by adding the CNF : (1) The hydrogen bond is formed by the -OH groups on the CNF surface and the -OH groups of cellulose, and increase the bonding area and bond strength between the fiber and the fiber. (2) CNF nano-level size will occur capillary action with the fibers when water filtering. (3) Nano-sized CNF is easy to fill in the pores between the fiber and fiber, resulting in network structure. (4) The larger the aspect ratio of the CNF has a higher strength to increase the reinforcing strength.

摘要 i
Abstract iii
目次 v
表目次 x
圖目次 xi
壹、前言 1
貳、文獻回顧 4
一、纖維素奈米材料的纖維來源 4
（一）木材纖維 4
（二）非木纖維 5
（三）動物纖維 5
（四）細菌纖維素（Bacterial cellulose；BC） 7
二、木材 7
（一）木材的化學組成 8
（二）纖維素 9
（三）微纖毛（Microfibril） 10
三、纖維素奈米材料 12
（一）纖維素奈米結晶（Cellulose nanocrystals；CNCs） 13
（二）微纖毛化纖維素 16
（三）纖維素奈米纖維 18
四、TEMPO氧化反應 21
（一）TEMPO藥劑 21
（二）TEMPO/NaBr/NaClO系統下的氧化反應 22
（三）TEMPO / NaClO / NaClO2系統下的氧化反應 24
（四）TEMPO電介導反應 26
（五）TEMPO氧化製備CNF的性質 27
五、纖維素奈米纖維之應用 29
（一）CNF在造紙上的應用 29
1. 對紙張濾水性的影響 29
2. CNF的添加對紙張性質的影響 30
（1）密度 30
（2）透氣度（Air permeability） 30
（3）光學性質 31
（4）強度 31
（二）表面塗布 32
（三）CNF/高分子複合材料 32
（四）CNF的表面疏水變性 33
（五）CNF作為吸附性材料 34
（六）CNF作為濾材 35
（七）光電應用 36
參、材料與方法 37
一、試驗材料 37
（一）纖維 37
（二）2,2,6,6-四甲基哌啶-1-氧基 37
（三）次氯酸鈉 37
（四）其他試驗用藥品 37
二、纖維素奈米纖維之製備 38
（一） TEMPO氧化纖維製備 38
1. 鹼性製備法 38
2. 中性製備法 38
三、羧基含量測定 39
四、TEMPO氧化纖維機械處理 40
（一）鹼性法 40
（二）中性法 41
五、纖維素奈米纖維性質的測定 41
（一）黏度測定及聚合度 41
1. 黏度測定 41
2. 纖維素奈米纖維之聚合度 42
（二）纖維素奈米纖維的透射率 42
（三）掃描電子顯微鏡（Scanning Electron Microscope；SEM）影像觀察 42
（四）原始纖維形態觀察 43
（五）傅立葉轉換紅外光譜（Fourier Transform Infrared Spectrometer；FT-IR） 43
（六）保水值（Water-retention value；WRV） 43
六、CNF添加於紙漿對抄製手抄紙性質的影響 43
（一）紙漿材料 43
（二）手抄紙的抄製 44
七、手抄紙物理性質測定 44
（一）厚度、密度 44
（二）不透明度 44
（三）光散射係數的測定 45
（四）平滑度 45
（五）透氣度 45
八、手抄紙機械性質測定 46
（一）抗張強度 46
（二）破裂強度 46
（三）撕裂強度 46
（四）耐折強度 47
九、統計分析 47
肆、結果與討論 48
一、TEMPO氧化在鹼性環境下製備纖維素奈米纖維 48
（一）氧化劑添加量對纖維素奈米纖維羧基含量和聚合度的影響 48
二、TEMPO氧化在中性環境下製備纖維素奈米纖維 49
（一）反應時間、氧化劑添加量對於羧基含量的影響 49
（二）反應時間、氧化劑添加量對於纖維素奈米纖維聚合度的影響 51
（三）中性TEMPO氧化反應的緩衝液的種類對CNF羧基含量的影響 53
三、TEMPO氧化纖維的保水值 54
四、纖維素奈米纖維的性質測定 56
（一）原始纖維和纖維素奈米纖維之形態比較 56
（二）CNF的光透射程度 56
（三） CNF的傅立葉轉換紅外光譜 59
五、添加不同聚合度的CNF對於紙張性質的影響 60
（一） CNF的種類 60
（二）一般性質 61
1. 紙張密度 61
2. 平滑度 62
3. 透氣抵抗 63
（三）光學性質 64
1. 不透明度 64
2. 光散射係數 65
（四）紙樣顯微影像觀察 66
（五）CNF的添加對手抄紙機械性質的影響 68
1. 抗張強度 68
2. 破裂強度 70
3. 撕裂強度 71
4. 耐折強度 72
伍、結論 75
陸、參考文獻 77

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