臺灣博碩士論文加值系統

本實驗目的在於製造高自由體積之水性PU粉末。傳統PU結構由高分子軟質段的多元醇與單體硬質段異氰酸鹽構成，鋪成膜後彈性與熱性質皆非常優異。水性PU則是在環保意識抬頭之後的產品，減少有機溶劑的使用。且由於奈米碳管被研究出具有高吸附氣體的效果，由於奈米碳管本身具有多苯環，因苯環之間的電子共振，藉以利用物理吸附而藉此吸附氣體，所以本實驗希望利用PANI的多苯環性質來吸附氣體，且由於PANI根據之前文獻吸附率達6~8%(48)。
本研究主題化合物為水性PU，Chen(11)等人發現，長硬質鏈段的水性PU，由於離子基會聚集，導致鏈段之間會出現孔隙，推測其孔隙可以吸附氫氣、氧氣或是二氧化碳。因考量到吸附性質需求孔隙要大，合成時將結構中的高分子鏈段以聚苯胺(Polyaniline)取代，合成出全硬段的高分子，以增加其孔隙。再藉由改變中和劑的長度，來增加其鏈上孔隙的大小，讓鏈與鏈之間的孔隙更大，增加其吸附的空間。本研究隨著聚苯胺上的苯環數目多寡和中和劑的分子量變化，觀察該材料的熱性質與吸附氣體能力。藉由其中的孔隙與和苯環之間的共振結構，是否對氫氣吸附有吸附效果，探討各組成的熱性質與吸附氣體能力。

The aim of this experiment is to produce powder which is composed by waterborne polyurethane of high free volume. Traditional PU structure consists of polyol of macromolecular soft segment and diisocyanate, thermal property and elasticity will become excellent after paved as membrane. Waterborne PU can be used to reduce the use of organic solvent, especially environment protection increasingly draws much attention.
And the nerocarbon tube is worked out having high result of absorbing the gas, because it is in charge of having many benzene rings. because the electronic resonance between the benzene ring itself enduring the nerocarbon tube, use to utilize physical absorption and absorb the gas by this, so the experiment hopes to utilize much benzene of PANI to absorb the gas, and because the reference said that PANI has ability to absorb hydrogen to 6~8%.
It was found by Chen[11] etc that Waterborne polyurethane of long hard segments produces holes among segments because ionic aggregates. As a result, it was inferred to be able to absorb hydrogen, oxygen and carbondioxid. Considering that better absorption ability needs larger holes, macromolecule of whole hard segments is synthesized to increase holes by substituting PANI for soft segment of macromolecule. By changing the length of the neutralizer, to increase the size of the hole on the chain, and let the hole between the chain and chain be bigger to increase its space absorbed.
This research, with changing the molecular weight of benzene and the length of neutralizer, observe heat property and hydrogen, oxygen, and carbondioxid absorption capabilities. With the hole among them and resonance structure between the benzene ring, whether absorb result of absorbing to the hydrogen, study the heat property and gas absorption capabilities

目錄
摘要I
英文摘要II
致謝III
目錄IV
圖目錄IX
表目錄XIII
第一章、序論1
1-1 前言1
1-2 研究與動機2
第二章、文獻回顧4
2-1 水性PU 的介紹4
2-1-1 PU 的結構4
2-1-2 水性PU 的分類5
2-1-3 親水基的導入5
2-1-3-1 陰離子型5
2-1-3-2 陽離子型6
2-1-3-3 非離子型7
2-1-3-4 陰陽離子共存型7
2-1-4 PU 離子體（PU ionomers)
2-1-5 PU 水性化的製程8
2-1-5-1 Solution process9
2-1-5-2 Prepolymer mixing process-9
2-1-5-3 Hot melt process10
2-1-5-4 Ketimine Ketimine process11
2-2 水性PU 的物理性質13
2-2-1 PU 分散液的水分散機制13
2-2-2 膠體粒子理論14
2-2-2-1 膠體的穩定性14
2-2-2-2 電雙層15
2-2-3 水性PU 的成膜性質18
2-2-4 水性PU Rheology19
2-2-4-1 黏度的定義19
2-2-4-2 流體的分類20
2-2-4-3 水性PU Rheology21
2-2-5 水性PU 的熱性質22
2-2-5-1 相轉變（phase transition)22
2-2-5-2 玻璃化轉變(glass transition)23
2-2-5-3 玻璃態(glass state)24
2-2-5-4 高彈態(rubbery state)24
2-2-5-5 黏流態(viscous state)25
2-2-5-6 黏流溫度(viscous flow temperature)25
2-2-5-7 熔點(melt point) Ｔm25
2-3 聚苯胺27
2-3-1 聚苯胺簡介27
2-3-2 聚苯胺的結構29
2-3-3 聚苯胺之化學合成32
2-3-4 聚合機構及氧化還原機制34
2.4 吸附理論36
2-4-1 吸附理論36
2-4-1-1 吸附平衡36
2-4-1-2 Langmuir等溫吸附37
2-4-1-3 BET等溫吸附39
2-4-1-4 Isothermal等溫曲線41
2-4-1-5吸附機構45
2-4-1-6 高分子吸附48
第三章 實驗部份51
3-1 化學藥品51
3-2 儀器設備51
3.3 實驗步驟52
3-3-1化合物合成52
3-3-1-1 polyaniline的合成方法52
3-3-1-2水性PU合成53
3-3-2 NCO 官能基濃度滴定(ASTM ASTM-D1368)54
3-3-3 氣體吸附實驗方法55
3-3-3-1 乾冰溫度下氫氣與氧氣吸附實驗55
3-3-3-2 液態氮溫度下氫氣吸附實驗56
3-4 分析方法56
3-4-1 FTIR56
3-4-2 TGA57
3-4-4 FE-SEM57
3-4-3 XRD58
3-4-4 DSC58
3-4-5 氣體吸附58
第四章 結果與討論59
4-1 討論的範圍59
4-1-1 改質軟段分子量59
4-1-2 中和劑長短59
4-2 PANI分子量鑑定60
4-3 FT-IR鑑定61
4-4 TGA分析67
4-5 SEM分析69
4-6 XRD分析75
4-7 DSC分析78
4-8 氣體吸附82
4-8-1氫氣於乾冰溫度下吸附82
4-8-2 氧氣於乾冰溫度下吸附87
4-8-3二氧化碳於冷凍機溫度(-70℃)下吸附91
4-8-4 氫氣於液態氮溫度下吸附95
第五章 結論99
參考文獻101

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