臺灣博碩士論文加值系統

烯類複分解聚合（Olefin metathesis polymerization）在高分子合成上是一個很重要的方法。近年來在高分子材枓的合成上，環烯類開環複分解聚合(ROMP)與非環二烯類複分解聚合(ADMET)為功能性高分子的合成打開新的一頁，其中包括帶各式官能基高分子材枓的合成。
帶有phthalimide基團的原冰片烯單體 (NBMPI)與含螢光基團的新型原冰片烯單體(NBMNA)以ROMP的方法合成聚合物，將其氫化、水解後可得胺基取代的原冰片烯聚合物。所得帶有胺基的聚合物幾乎不溶於一般有機溶劑，以氯化氫氣體四級化為銨基後可溶於水中，得到一水溶性高分子。藉由導入的螢光集團，研究其光物理現象。並就其水溶液性質包括黏度、表面張力及螢光行為作討論。
再將NBMPI與1,5-cyclooctadiene (COD) 以ROMP的方法利用不同比例之單體及觸媒比合成不同分子量及鍊段長的共聚合物。並將其氫化得氫化後嵌段共聚合物，比較氫化前後溶解性及熱性質的不同。其中poly(NBMPI-b-PB)-1可進行水解及四級化製備水溶性高分子[poly(HCQNBMA-b-PB)-1]，研究其水溶性物性的變化（包括界面現象、粒徑測量等…）。
合成一帶有Carbazole基團的原冰片烯衍生物5-(N-carbazolyl methyl)bicyclo[2.2.1]hept-2-ene (CbzNB)，用鐒觸媒{RuCl2(CHPh)[P(C6H11)3]2}與1,5-cyclooctadiene (COD) 利用不同比例之單體及觸媒比合成不同分子量及鍊段長的共聚合物。並將其氫化得氫化後嵌段共聚合物，所得共聚合物以核磁共振光譜、紅外線光譜、螢光光譜等加以鑑定。氫化後可提高共聚合物之熱安定性。
將CbzNB與NBMPI用鐒觸媒{RuCl2(CHPh)[P(C6H11)3]2}進行活性開環複分解聚合，改變不同比例之單體及觸媒比，合成三種不同分子量及鍊段長的共聚合物。在各別將其氫化，得氫化後嵌段共聚合物，就其分子量分佈、螢光、溶解度及熱穩定性討論之。
由原冰片烯甲醇與甲基丙烯醯氯 (methacryloyl chloride)在低溫下作用得一具有環烯與末端烯類的新單體[5-(methyl methacryloyl)bicyclo[2.2.1]hept-2-ene] (NBMM)，以ROMP的方法聚合，得到側鏈帶有甲基丙醯基團的聚合物。將側鏈帶有甲基丙醯基團的聚合物與甲基丙醯酸甲酯(MMA)進行熱聚合反應，得到AB交聯的共聚合物，以提高聚合物之熱穩定性。
帶有環氧基團的原冰片烯單體(NBepoxy)以ROMP的方法用{RuCl2(CHPh)[P(C6H11)3]2}為觸媒合成聚合物，所得聚合物以核磁共振光譜、紅外線光譜等加以鑑定。改變不同比例之單體及觸媒比，討論其分子量及分子量分佈情形。

The olefin metathesis reaction is of great synthetic utility in polymer chemistry. The recent developments of ring-opening metathesis polymerization (ROMP) and acyclic diene metathesis (ADMET) have open new avenues for synthesis a variety of polymeric materials, including polymers bearing functional groups.
5-(Phthalimide methyl)bicyclo[2.2.1]hept-2-ene (NBMPI) and 5-(methoxylnaphthalene)bicyclo[2.2.1]hept-2-ene (NBMNA) were prepared to synthesize a amino group containing poly(norbornene) via living ring-opening metathesis polymerization (ROMP) by using a well-defined ruthenium catalyst {RuCl2(CHPh)[P(C6H11)3]2}. Poly(HNBMA)/NA could be obtained after hydrogenation and hydrolysis. Poly(HNBMA)/NA is insoluble in common organic solvents; however, water-soluble naphthalene-labeled poly(HCQNBMA)/NA could be obtained after quaternization of the amine groups by gaseous HCl. The aqueous solution properties of poly(HCQNBMA)/NA are examined the behavior of viscosity, surface tension and fluorescence.
The new diblock copolymers having different molecular weight of 5-(phthalimide methyl)bicyclo[2.2.1]hept-2-ene (NBMPI) with 1, 5-cyclooctadiene (COD) have been successful synthesized by ROMP using well-defined {RuCl2(CHPh)[P(C6H11)3]2} as catalyst. And the molecular weight can be regulated easily by changing the ratio of monomer to catalyst. Their hydrogenated derivatives were been obtained by using p-toluenesulfonylhydrazide as a hydrogenation agent. The synthesis, solubility, thermal properties were investigated. Poly[(hydrochloride quaternized 2-norbornene-5-methyleneamine)-b-butadiene]-1, poly(HCQNBMA-b-PB)-1, has also been prepared, followed by hydrolysis and quaternization of poly(NBMPI-b-PB)-1. The synthesis, surface tension, and solution properties were also studied.
A new carbazole-functionalized norbornene derivative, 5-(N-carbazolyl methyl) bicyclo[2.2.1]hept-2-ene (CbzNB), was polymerized with 1, 5-cyclooctadiene (COD) via living ring-opening metathesis polymerization (ROMP) by using {RuCl2 (CHPh)[P(C6H11)3]2}. The diblock copolymers having different molecular weight and segments could be obtained by changing the ratio of monomer to catalyst. Hydrogenated copolymers would be obtained by using p-toluenesulfonylhydrazide as a hydrogenation agent. The diblock copolymers were characterized by means of 1H NMR, infrared spectra, and fluorescence. Saturation of the main chain double bonds increases the thermal stability of the polymer.
Ring-opening metathesis polymerization (ROMP) has been performed with {RuCl2(CHPh)[P(C6H11)3]2} catalyst to make low polydispersity block copolymers of CbzNB and NBMPI. Three diblock copolymers with the CbzNB and NBMPI were made, varying both molecular weight and percent of each block. The hydrogenated diblock copolymers were successfully obtained by using p-toluenesulfonylhydrazide as a reducing agent. The synthesis, molecular weight distributions, solubility, thermal stability were investigated.
Novel monomer 5-(methyl methacryloyl)bicyclo[2.2.1]hept-2-ene (NBMM) having cyclic olefin and terminal double bond was prepared from 5-(hydroxymethyl)bicyclo[2.2.1]hept-2-ene and methacryloyl chloride at 0~5℃. The ring-opening metathesis polymerization (ROMP) of NBMM was investigated to produce polymer with cross-linkable side chain by using {RuCl2(CHPh)[P(C6H11)3]2} catalyst. The AB cross-linked material was accomplished through the reaction of poly(NBMM) with methacryloyl side chains and methyl methacrylate (MMA) by thermal polymerization to enhance the thermal stability.
Norbornene (bicycol[2.2.1]hept-2-ene) monomer containing epoxy group, 5-(glycidyl ether)bicyclo[2.2.1]hept-2-ene (NBepoxy), can be polymerized by well-defined ruthenium complex {RuCl2(CHPh)[P(C6H11)3]2} as catalyst via ring-opening metathesis polymerization (ROMP). The resulting polymers were characterized by infrared spectra (IR), 1H NMR, and 13C NMR. The polymers having different molecular weight and molecular weight distribution could be obtained by changing the ratio of monomer to catalyst.

第一章 Effect of Various Salts and Surfactant on Aqueous Solution Properties of Naphthalene-labeled Poly(hydrochloride quaternized 2-norbornene-5-methylamine) -------------------------------------------------------------- ---- 1
1.1 ABSTRACT -----------------------------------------------------------------------------------1
1.2 INTRODUCTION ----------------------------------------------------------------------------1
1.3 EXPERIMENTAL----------------------------------------------------------------------------3
1.3.1 Materials ---------------------------------------------------------------------------------3
1.3.2 Monomer synthesis --------------------------------------------------------------------3
1.3.3 Polymerization ------------------------------------------------------------------------- 4
1.4 CHARACTERIZATION METHODS ------------------------------------------------------9
1.4.1 Viscometric measurements -----------------------------------------------------------9
1.4.1 Fluorescence spectra ------------------------------------------------------------------ 9
1.5 RESULTS AND DISCUSSION -----------------------------------------------------------10
1.5.1 Viscosity study of poly(HCQNBMA)/NA-----------------------------------------10
1.5.2 Surface activity of poly(HCQNBMA)/NA in various salts---------------------14
1.5.3 Fluorescence quenching study of poly(HCQNBMA)/NA-----------------------17
1.5.4 Proposed model for poly(HCQNBMA)/NA in aqueous soluion---------------24
1.6 CONCLUSIONS --------------------------------------------------------------------------25
1.7 REFERENCES -------------------------------------------------------------------------------27
第二章 Synthesis and Characterization of New Diblock Copolymers Derived from 5-(Phthalimide methyl)bicyclo[2.2.1]hept-2-ene and 1, 5-Cyclooctadiene Using Ring-Opening Metathesis Polymerization (ROMP) ---------------30
2.1 ABSTRACT ----------------------------------------------------------------------------------30
2.2 INTRODUCTION ---------------------------------------------------------------------------31
2.3 EXPERIMENTAL ---------------------------------------------------------------------------32
2.3.1 Materials --------------------------------------------------------------------------------32
2.3.2 Monomer synthesis ------------------------------------------------------------------- 33
2.3.3 Polymerization -------------------------------------------------------------------------33
2.4 CHARACTERIZATION METHODS ----------------------------------------------------36
2.5 RESULTS AND DISCUSSION -----------------------------------------------------------42
2.5.1 Characterization of diblock copolymers -------------------------------------------42
2.5.2 Solubility characteristics -------------------------------------------------------------44
2.5.3 Thermal stability ----------------------------------------------------------------------46
2.5.4 Surface tension ------------------------------------------------------------------------47
2.5.5 Dynamic light scattering -------------------------------------------------------------51
2.6 CONCLUSIONS ----------------------------------------------------------------------------52
2.7 REFERENCES -------------------------------------------------------------------------------57
第三章 Synthesis and Characterization of New Diblock Copolymers of 5-(N-Carbazolyl methyl)bicyclo[2.2.1]hept-2-ene and 1, 5-Cyclooctadiene (COD) Using Ring-Opening Metathesis Polymerization (ROMP) ----- 59
3.1 ABSTRACT ----------------------------------------------------------------------------------59
3.2 INTRODUCTION ---------------------------------------------------------------------------60
3.3 EXPERIMENTAL ---------------------------------------------------------------------------61
3.3.1 Materials -------------------------------------------------------------------------------61
3.3.2 Monomer synthesis -------------------------------------------------------------------62
3.3.3 Polymerization -------------------------------------------------------------------------62
3.4 CHARACTERIZATION METHODS ----------------------------------------------------64
3.5 RESULTS AND DISCUSSION -----------------------------------------------------------66
3.5.1 Characterization of diblock copolymers -------------------------------------------66
3.5.2 UV, fluorescence, hydrodynamic diameters of the copolymers -----------------72
3.5.3 Solubility characteristics -------------------------------------------------------------72
3.5.4 Thermal stability ----------------------------------------------------------------------73
3.6 CONCLUSIONS ----------------------------------------------------------------------------78
3.7 REFERENCES -------------------------------------------------------------------------------79
第四章 Living Ring-Opening Metathesis Polymerization (ROMP) for the Preparation of Novel Diblock Copolymers of 5-(N-Carbazolyl methyl) bicyclo[2.2.1]hept-2-ene and 5-(Phthalimide methyl)bicyclo[2.2.1]hept-2-ene --------------------------------------------------------------------------------- 81
4.1 ABSTRACT ---------------------------------------------------------------------------------81
4.2 INTRODUCTION ---------------------------------------------------------------------------82
4.3 EXPERIMENTAL ---------------------------------------------------------------------------83
4.3.1 Materials --------------------------------------------------------------------------------83
4.3.2 Monomer synthesis -------------------------------------------------------------------84
4.3.3 Polymerization ------------------------------------------------------------------------84
4.4 CHARACTERIZATION METHODS ----------------------------------------------------86
4.5 RESULTS AND DISCUSSION -----------------------------------------------------------88
4.5.1 Polymerization and characterization of diblock copolymers -------------------88
4.5.2 Fluorescence of diblock copolymers------------------------------------------------95
4.5.3 Solubility characteristics-------------------------------------------------------------95
4.5.4 Thermal stability----------------------------------------------------------------------98
4.6 CONCLUSIONS ---------------------------------------------------------------------------99
4.7 REFERENCES -----------------------------------------------------------------------------101
第五章 Synthesis and Characterization of New Cross-Linkable Polynorbornene Having Methacryloyl Group via Ring-Opening Metathesis Polymerization (ROMP) ---------------------------------------------------------------------------102
5.1 ABSTRACT -------------------------------------------------------------------------------- 102
5.2 INTRODUCTION ------------------------------------------------------------------------- 102
5.3 EXPERIMENTAL ------------------------------------------------------------------------- 104
5.3.1 Materials ------------------------------------------------------------------------------104
5.3.2 Monomer synthesis ------------------------------------------------------------------104
5.3.3 Ligand exchange of catalyst(II) with MMA or with 1-pentene ---------------104
5.3.4 Equimolar reaction between catalyst(II) and NBMM---------------------------105
5.3.5 Polymerization -----------------------------------------------------------------------106
5.4 CHARACTERIZATION METHODS ---------------------------------------------------107
5.5 RESULTS AND DISCUSSION ----------------------------------------------------------111
5.5.1 Initial polymerization studies ----------------------------------------------------111
5.5.2 Influence of various ligands --------------------------------------------------------113
5.5.3 Characterization of the poly(NBMM) --------------------------------------------116
5.5.4 Synthesis of AB cross-linked systems of poly(NBMM) and polyMMA-----116
5.6 CONCLUSIONS ---------------------------------------------------------------------------117
5.7 REFERENCES -----------------------------------------------------------------------------121
第六章 Synthesis and Properties of Novel Polynorbornene Bearing Epoxy Moiety via Ring-Opening Metathesis Polymerization (ROMP) -------------------122
6.1 ABSTRACT --------------------------------------------------------------------------------122
6.2 INTRODUCTION -------------------------------------------------------------------------122
6.3 EXPERIMENTAL-------------------------------------------------------------------------123
6.3.1 Materials -----------------------------------------------------------------------------123
6.3.2 Monomer synthesis ------------------------------------------------------------------124
6.3.3 Polymerization -----------------------------------------------------------------------124
6.4 CHARACTERIZATION METHODS ---------------------------------------------------125
6.5 RESULTS AND DISCUSSION ----------------------------------------------------------129
6.5.1 Characterization of the poly(NBepoxy) ------------------------------------------129
6.5.2 Solubility characteristics and thermal stability ----------------------------------129
6.6 CONCLUSIONS ---------------------------------------------------------------------------130
6.7 REFERENCES -----------------------------------------------------------------------------132
附錄 --------------------------------------------------------------------------------------------- 133
作者簡介----------------------------------------------------------------------------------------- 135
授權書-------------------------------------------------------------------------------------------- 136

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