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研究生:胡春霞
研究生(外文):Hu, chun-hsia
論文名稱:含PEG雙性梳狀高分子之合成與物性探討
論文名稱(外文):Synthesis and Characterization of PEG-containing Amphiphilic Comb Copolymers
指導教授:陳崇賢陳崇賢引用關係
指導教授(外文):Chern Chorng Shyan
學位類別:碩士
校院名稱:國立台灣工業技術學院
系所名稱:化學工程技術研究所
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:1997
畢業學年度:85
語文別:中文
論文頁數:140
中文關鍵詞:聚乙二醇單甲基醚雙性高分子微胞臨界微胞濃度焦油腦
外文關鍵詞:PEGamphiphilic copolymermicelleCMCpyrene
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本研究利用聚乙二醇單甲基醚(polyethylene glycol,PEG)上之羥
基和丙烯醯氯(acry loyl chloride)上之氯化醯基以三乙胺為酸接受劑
進行縮和反應, 合成一具丙烯醯基之聚乙二醇單體(acryloyl PEG),
再將此單體和十八烷基甲基丙烯酸甲酯(stearyl meth acrylate)(或
十二烷基甲基丙烯酸甲酯(lauryl methacrylate)及丙烯酸(或丙烯
酸正丁酯、二羥基甲基丙烯酸甲酯),以偶氮二異丁(AIBN)為起始劑,
甲苯為溶劑,於 70 ℃ 下進行自由基加成聚合反應,合成具親水基及疏
水基之雙性高分子。 經沉澱、超過濾純化步驟後,所得之梳狀高分子,
以IR、1H-NMR、GPC 檢測其純化效果,並以 GPC 測量梳狀高分子之相對
分子量(標準品為 Polystyrene ),由1H-NMR 圖譜積分值計算組成,光
散射方法測量水中微胞之分子量,螢光圖譜檢測臨界微胞濃度、及高分子
對焦油腦之重量平均分配係數。使 用所得之高分子分子量、相對莫耳組
成、高分子微胞之集結數、重量平均分配係數、CMC 等,來計算各個梳
狀高分子產物之理論水力半徑,及比較各個梳狀高分子產物之親疏水性性
質。 所得梳狀高分子之 CMC 約在 10-4 ~ 10-3 g/ml,高分子微胞之
集結數範圍為 217 ~ 3664,理論水利半徑在 29 nm~56 nm (實驗值小於
理論值 18.97 nm ~ 26.07nm)。在比較各個梳狀高分子產物之親疏水性質
之過程中,發現主鍊 AA 對於梳狀高分子之親疏水性質並無很大的影響。
於焦油腦螢光消光實驗結果中,推測本實驗所得之高分子微胞的結構應可
分為四相,(1)核心(2)AA 層(3)PEG 層 、及(4)水相,焦油腦在
此四相中分配之平衡關係應是各相之間達平衡,但此結構為一推測尚無法
以實驗驗證。而高分子微胞對焦油腦之包覆率,以螢光消光的實驗結果顯
示,在加入之焦油腦濃度低於水中飽和濃度時,高分子微胞對焦油腦之包
覆率可高達 94 % 以上,而在焦油腦濃度高於水中飽和濃度之 14 ~ 32
倍時,高分子微胞對焦油腦之包覆率也可達 67 ~ 97 %,所以本實驗所合
成之高分子微胞具包覆大量的疏水性物質之特性。

Amphiphilic copolymers based on stearyl methacrylate (or
lauryl methacrylate),acrylic acid (or 2-hydroxyethyl
methacrylate, or n-butyl acrylate), and poly ( ethylene glycol)
acrylate were sythesized and their properties in aqueous systems
investigated. The molecular weights of these copolymer were
analyzed by gel permeation chromatography . Molecular weights
and particle sizes of polymeric micelles were characterized by
static and dynamic light scattering as well. In addition, the
compositions of the comb coolymers were determined by NMR.
The aggregation numbers of micelles were ranged from 217 to
3664 . The number of PEG and alkyl chains per molecule was found
to be 5 ~ 18 and 6 ~ 16, respectively.
Two fluorimetric techniques were used to characterize the
properties of the aqueous solutions of micelles . The first
method was based on the measurements of the ratio of intensities
of the third and first vibrational bands, I3/I1, in the emission
spectra of pyrene solubilized in a micellar solution as a
function of micellar concentration. The strong perturbation of
the vibronic band intensities was used as probe to accurately
determine critical micelle concentrations. The second method was
based on the queching of fluorescence from solubilized pyrene by
Cu2+. The quench technique can give the pyrene loading capcity
data. The loading capacity was found to be above 94 % whenthe
pyrene concentration was lower than its saturated concentration.
When the pyrene concentration was 14 ~ 32 times higher than its
saturated concentration the loading capacity was in the range
of 67 ~ 97 % .
The study of CMC, Nagg, HLB, and compsition of copolymers
indicated thatthe formation of micelles was primarily determined
by the hydrophobic / hydrophilic properties of these
copolymers. In comparison with the hydrophobic / hydrophilic
properties of these copolymers, we found that PEG and Alky(R)
composition is the key factor.

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