臺灣博碩士論文加值系統

本實驗使用可逆加成斷鏈鏈轉移聚合法(RAFT)合成高分子，所使用之RAFT試劑為雙苯甲基三硫碳酸酯(DBTTC)，合成DBTTC經由13C-NMR、1H-NMR、DSC，確定其結構、純度、熔點，利用DBTTC進行活性聚合法，首先使用甲苯為溶劑，單體為苯乙烯，在60℃、70℃、80℃、100℃溫度下反應，由於有溶劑及起始劑影響，分子量分佈在1.4-1.8間。以總體聚合在80℃、110℃溫度，不同的RAFT試劑與起始劑莫爾比，少了溶劑影響，分子量分佈在1.4-1.69。單純使用熱聚合100℃、110℃、120℃，在未加入RAFT試劑所造成分子量大，且分子量分佈寬(PDI>2)，加入不同比例RAFT試劑，隨著RAFT試劑濃度增加分子量下降，分子量分佈在1.25-1.35，再加入相同單體苯乙烯做鏈延伸，分子量增加，分子量分佈為1.47。加入2-乙基丙烯酸丁酯(2-EHA)，合成嵌段高分子，使用不同起始劑AIBN、BPO，在80℃分子量比110℃大，而分子量分佈則為1.8-2.3。

Reversible addition-fragmentation chain transfer(RAFT) polymerization was investigated.The RAFT agent used dibenzyltrithiocarbonate (DBTTC).13C-NMR、1H-NMR、DSC were used to verify the structure,purity,and melting point of DBTTC.In RAFT polymerization with DBTTC,toluene was used as solvent,and styrene used as monomer.The molecular weight distribution attained is in the range 1.4-1.8 due to solvent and initiator effects at 60℃,70℃,80℃,and 100℃.Using bulk polymerization,the ratio of RAFT agent to initiator was varied,and molecular weight distribution is in the range 1.4-1.69 at 80℃,and 110℃.In thermal polymerization at 100℃,110℃,and 120℃,the product in the absence of RAFT agnet has a very high molecular weight,and molecular weight distribution is very broad(PDI>2).With different levels of RAFT agent,molecular weight distribution is in the range 1.25-1.35.Chain extension with the same monomer results higher in molecular weight,and a broader distribution(PDI=1.47).Block polymer was prepared by using 2-Ethylhexyl Acrylate(2-EHA) and different initiators.At 80℃,molecular weight is bigger than 110℃.The molecular weight distribution is in the range 1.8-2.3.

目錄
中文摘要………………………………………………………………I
英文摘要………………………………………………………………II
誌謝
表目錄…………………………………………………………………VI
圖目錄…………………………………………………………………VII
第一章 序論……………………………………………………………1
1-1 活性自由基聚合簡介………………………………………1
1-2 活性自由基聚合的種類…………………………………1
1-3 研究目的………………………………………………………3
第二章 文獻回顧………………………………………………………5
2.1 可逆加成-斷裂鏈轉移聚合法(RAFT)………………………5
2.2 副反應…………………………………………………………8
2.3 鏈轉移常數影響………………………………………………9
2.4 三硫代化合物………………………………………………14
2.5 三嵌段(triblock)線性高分子……………………………16
2.6 活性自由基共聚合反應……………………………………17
2.7 RAFT迷你乳液聚合反應…………………………………19
2.8 活性聚自由基聚合應用……………………………………20
第三章 實驗藥品與步驟……………………………………………22
3-1 實驗藥品……………………………………………………22
3-2 實驗儀器與設備……………………………………………25
3-3 實驗流程與步驟……………………………………………27
3-3-1 合成RAFT試劑………………………………………27
3-3-2 RAFT活性自由基聚合………………………………29
3-3-3 活性巨鏈轉移劑溶液聚合……………………………30
3-3-4 活性巨鏈轉移劑總體聚合……………………………31
3-3-5 巨鏈轉移劑鏈延伸……………………………………35
3-3-6 三嵌段(triblock)高分子合成………………………36
3-4 轉化率計算……………………………………………………39
3-5 理論分子量計算………………………………………………39
第四章 結果與討論……………………………………………………40
4-1 鏈轉移試劑DBTTC鑑定分析………………………………40
4-2 活性巨鏈轉移劑(MacroCTA)製備…………………………44
4-2-1 以溶劑法製備巨鏈轉移劑……………………………44
4-2-2 以總體聚合製備巨鏈轉移劑…………………………47
4-2-3 以總體聚合之熱聚合製備巨鏈轉移劑………………51
4-3 巨鏈轉移劑鏈延伸……………………………………………57
4-4 三嵌段聚合物…………………………………………………60
第五章 結論……………………………………………………………64
第六章 建議與未來工作…………………………………….……….66
參考文獻
附錄

1.T.P.Le,G.Moad,E.Rizzardo,S.H.Thang,“Polymerization with
living characteristics”,PCT Int.App.WO9801478 A1980115(1998)
2.Y.K.Chong,T.P.Le,G.Moad,E.Rizzardo,S.H.Thang,“A More Versatile Route to Block Copolymers and Other Polymers of Architecture by Living Radical Polymerization:The RAFT Process”,Macromolecules,32,2071-2074(1999)
3.J.Chiefari,Y.K.Chong,F.Erocle,J.Krstina,J.Jeffery,T.P.Le,
R.T.A.Mayadunne,G.F.Meijs,C.L.Moad,G.Moad,E.Rizzardo,S.H.Thang,“Living Free-Radical Polymerization by Reversible Addition-Fragmentation Chain Transfer:The RAFT Process”,Marcomolecules,31,5559-5562(1998)
4.R.Severac,P.Lacroix-Desmazes,B.Boutevin,“Reversible addition-fragmentation chain-transfer(RAFT)copolymerization of vinylidene chloride and methyl acrylate”,Polym Int,51,1117-1122(2002)
5.A.Goto,K.Sato,Y.Tsujii,T.Fukuda,G.Moad,E.Rizzardo,S.H.Thang,“Mechanism and Kinetics of RAFT-Based Living Radical Polymerizations of Styrene and Methyl Methacrylate”,Macromolecules,34,402-408(2001)
6.S.Perrier,C.Barner-Kowollik,J.F.Quinn,P.Vanna,T.P.Davis,“Origin of Inhibition Effects in the Reversible Addition Fragmentation Chain Transfer(RAFT)Polymerization of Methyl Acrylate”,Macromolecules,35,8300-8306(2002)
7.C.Barner-Kowollik,J.F.Quinn,T.L.U.Nguyen,J.P.A.Heuts,
T.P.Davis,“Kinetic Investigations of Reversible Addition Fragmentation Chain Transfer Polymerization:Cumyl Phenyldithioacetate Mediated Homopolymerization of Styrene and Methyl Methyl methacrylate”,Macromolecules,34,7849-7857(2001)
8.C.Barner-Kowollik,“Handbook of RAFT Polymerization”,Wiley(2008)
9.G.Moad,E.Rizzardo.S.H.Thang“Living Radical Polymerization by the RAFT Process”,Aust.J.Chem.,58,379-410(2005)
10.M.J.Monteiro,H.de Brouwer,“Intermediate Radical Termination as the Mechanism for Retardation in Reversible Addition-Fragmentation Chain Transfer Polymerization”,Macromolecules,34,349-352(2001)
11.M.J.Monteiro,“Design Strategies for Controlling the Molecular Weight and Rate Using Reversible Addition-Fragmentation Chain Transfer Mediated Living Radical Polymerization”,Polym Sci Part A:Polym chem,43,3189-3204(2005)
12.G.Moad,J.Chiefari,Y.K.Chong,J.Krstina,R.T.A.Mayadunne,A.Postma,E.Rizzardo,S.H.Thang,“Living free radical polymerization with reversible addition-fragmentation chain transfer(the life of RAFT)”,Polym Int,49,993-1001(2000)
13.C.L.Moad,G.Moad,E.Rizzardo,S.H.Thang,“Chain Transfer Activity ofω-Unsaturated Methyl Methacrylate Oligomers”,Macromolecules,29,7717-7726(1996)
14.A.H.E.Müller,R.Zhuang,D.Yan,G.Litvinenko,“Kinetic Analysis of“Living”Polymerization Processes Exhibiting Slow Equilibria.1. Degenerative Transfer (Direct Activity Exchange between Active and“Dormant”Species).Application to Group Transfer Polymerization”,Macromolecules,28,4326-4333(1995)
15.Y.K.Chong,J.Krstina,T.P.T.Le,G.Moad,A.Postma,E.Rizzardo,S.H.Thang,“Thiocarbonylthio Compounds [S=C(Ph)S-R] in Free Radical Polymerization with Reversible Addition-Fragmentation Chain Transfer (RAFT Polymerization).Role of the Free-Radical Leaving Group (R)”,Macromolecules,36,2256-2272(2003)
16.G.Moad,E.Rizzardo,S.H.Thang,“Radical addition-fragmentation chemistry in polymer synthesis”,Polymer,49,1079-1131(2008)
17.J.M.Lee,O.H.Kim,S.E.Shim,B.H.Lee,S.Choe,“Reversible Addition-Fragmentation Chain Transfer (RAFT) Bulk Polymerization of Styrene : Effect of R-Group Structures of Carboxyl Acid Group Functionalized RAFT Agents”,Macromolecular Research,13,236-242(2005)
18.S.E.Shim,H.Jung,H.Lee,J.Biswas,S.Choe,“Living radical dispersion photopolymerization of styrene by a reversible Addition-fragmentation chain transfer(RAFT)agent”,Polymer,44,5563-5572(2003)
19.R.T.A.Mayadunne,E.Rizzardo,J.Chiefari,J.Krstina,G.Moad,A.Postma,S.H.Thang,“Living Polymers by the Use of Trithiocarbonates as Reversible Addition-Fragmentation Chain Transfer(RAFT)Agents:ABA Triblock Copolymers by Radical Polymerization in Two Steps”,Macromolecules,33,243-243(2000)
20.X.H.Liu,G.B.Zhang,X.F.Lu,J.Y.Liu,D.Pan,Y.S.Li“Dibenzyl Trithiocarbonate Mediated Reversible Addition–Fragmentation Chain Transfer Polymerization of Acrylonitrile”,Polym Sci Part A:Polym chem,44,490-498(2006)
21.J.J.Yuan,R.Ma,Q.Gao,Y.F.Wang,S.Y.Cheng,L.X.Feng,Z.Q.Fan,L.Jiang,“Synthesis and Characterization of Polystyrene/Poly(4-vinylpyridine) Triblock Copolymers by Reversible Addition–Fragmentation Chain Transfer Polymerization and Their Self-Assembled Aggregates in Water”,J.Appl.Polym.Sci.,89,1017-1025(2003)
22.J.Adelsberger,A.Kulkarni,A.Jain,W.Wang,A.M.Bivigou-Koumba,P.Busch,V.Pipich,O.Holderer,T.Hellweg,A.Laschewsky,P.Müller-Buschbaum,C.M.Papadakis,“Thermoresponsive PS-b-PNIPAM-b-PS Micelles: Aggregation Behavior,Segmental Dynamics, and Thermal Response”,Macromolecules,43,2490-2501(2010)
23.A.M.Bivigou-Koumba,J.Kristen,A.Laschewsky,P.Müller-Buschbaum,C.M.Papadakis,“Synthesis of Symmetrical Triblock Copolymers of Styrene and N-isopropylacrylamide Using Bifunctional Bis(trithiocarbonate)s as RAFT Agents”,
Macromol.Chem.Phys.,210,565-578(2009)
24.Y.Mitsukami,M.S.Donovan,A.B.Lowe,C.L.Mccormick,“Water-Soluble Polymers. 81. Direct Synthesis of Hydrophilic Styrenic-Based Homopolymers and Block Copolymers in Aqueous Solution via RAFT”,Macromolecules,34,2248-2256(2001)
25.Y.Mitsukami,A.Hashidzume,S.I.Yusa,Y.Morishima,A.B.Lowe,
C.L.Mccormick,“Characterization of pH-dependent micellization of polystyrene-based cationic block copolymers prepared by reversible addition-fragmentation chain transfer (RAFT) radical polymerization”,Polymer,47,4333-4340(2006)
26.R.H.Lambeth,S.Ramakrishnan,R.Mueller,J.P.Poziemski,G.S.Miguel,L.J.Markoski,C.F.Zukoski,J.S.Moore,“Synthesis and Aggregation Behavior of Thermally Responsive Star Polymers”,Langmuir,22,6352-6360(2006)
27.Y.Li,B.S.Lokitz,C.L.Moccormick,“RAFT Synthesis of a Thermally Responsive ABC Triblock Copolymer Incorporating N-Acryloxysuccinimide for Facile in Situ Formation of Shell Cross-Linked Micelles in Aqueous Media”,Macromolecules,39,81-89(2006)
28.W.Steinhauer,R.Hoogenboom,H.Keul,M.Moeller,“Copolymerization of 2-Hydroxyethyl Acrylate and 2-Methoxyethyl Acrylate via RAFT: Kinetics and Thermoresponsive Properties”,Macromolecules,43,7041-7047(2010)
29.Y.Z.You,C.Y.Hong,C.Y.Pan,“Controlled alternating copolymerization of St with MAh in the presence of DBTTC”,European Polymer Journal,38,1289-1295(2002)
30.M.K.Georges,R.P.N.Veregin,P.M.Kazmaier,G.K.Hamer,“Narrow Molecular Weight Resins by a Free-Radical Polymerization Process”,Macromolecules,26,2987-2988(1993)
31.B.Keoshkerian,M.K.Georges,D.Boils-Boisser,“Living Free-Radical Aqueous Polymerization”,Macromolecules,28,6381-8382(1995)
32.J.S.Wang,K.Matyjaszewski,“Controlled/"Living"Radical Polymerization.Halogen Atom Transfer Radical Polymerization Promoted by a Cu(I)/Cu(II) Redox Process”,Macromolecules,28,7901-7910(1995)
33.V.Percec,H.J.Kim,B.Barboiu,“Disulfonyl Chlorides: A Universal Class of Initiators for Metal-Catalyzed“Living”Diradical Polymerization of Styrene(s),Methacrylates,and Acrylates”,Macromolecules,30,6702-6705(1997)
34.王振希,張慶華,詹曉力,陳豐秋,熊繼海,“苯乙烯可逆加成-斷裂鏈轉移聚合動力學”,化工學報,61,4(2010)
35.Y.Luo,X.Liu,“Reversible Addition–Fragmentation Transfer(RAFT) Copolymerization of Methyl Methacrylate and Styrene in Miniemulsion”,Polym Sci Part A:Polym chem,42,6248-6258(2004)
36.L.Yang,Y.Luo,B.Li,“RAFT Miniemulsion Polymerization Targeting to Polymer of Higher Molecular Weight”,
Polym Sci Part A:Polym chem,43,4972-4979(2005)
37.L.Yang,Y.Luo,B.Li,“Reversible addition fragmentation transfer(RAFT) polymerization of styrene in a miniemulsion: A mechanistic investigation”,Polymer,47,751-762(2006)
38.M.Lansalot,T.P.Davis,J.P.A.Heuts,“RAFT Miniemulsion Polymerization: Influence of the Structure of the RAFT Agent”,Macromolecules,35,7582-7591(2002)
39.G.Moad,D.H.Solomon,“The chemistry of free radical polymerization”,Elsevier Science,(1995)
40.R.T.A.Mayadunne,E.Rizzardo,J.Chiefari,Y.K.Chong,G.Moad,S.H.Thang,“Living Radical Polymerization with ReversibleAddition-Fragmentation Chain Transfer(RAFT Polymerization)Using Dithiocarbamates as Chain Transfer Agents”,Macromolecules,32,6977-6980(1999)
41.Y.Kwak,A.Goto,T.Fukuda,“Rate Retardation in Reversible Addition-Fragmentation Chain Transfer(RAFT)Polymerization:Further Evidence for Cross-Termination Producing 3-Arm Star Chain”,
Macromolecules,37,1219-1225(2004)
42.J.Qiu,B.Charleux,“Controlled/living radical polymerization in aqueous media:homogeneous and heterogeneous systems”,Prog.Polym.Sci.,26,2083-2134(2001)
43.許毓倫,“以RAFT活自由基乳化聚合法合成用於不飽和聚酯、乙烯基酯及環氧樹酯之奈米級及次微米級高分子核殼型橡膠添加劑”,台灣科技大學化工系研究所(2012)
44.M.L.Senyek,J.J.Kulig,“Dibenzyltrithiocarbonate Molecular Weight Regulator for Emulsion Polymerization”,US Patent 6,369,158(2002)
45.S.Fre ́al-Saison,M.Save,C.Bui,B.Charleux,S.Magnet“Emulsifier-Free Controlled Free-Radical Emulsion Polymerization of Styrene via RAFT Using Dibenzyltrithiocarbonate as a Chain Transfer Agent and Acrylic Acid as an Ionogenic Comonomer:Batch and Spontaneous Phase Inversion Processes”,Macromolecules,39,8632-8638(2006)