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研究生： 林優恩
Hyurin - Oktavia
論文名稱： 奈米級及次微米級核殼型橡膠添加劑、無機二氧化矽/有機高分子核殼型顆粒、及蒙特納石黏土對不飽和聚酯、乙烯基酯、及環氧樹脂之聚合固化反應動力、玻璃轉移溫度、体積收縮及內部可染色性之影響研究
Effects of Nano-scale and Submicron-scale Core-shell Rubber Additives, Inorganic Silica/Organic Polymer Core-shell Particle, and Montmorillonite Clay on the Cure Kinetics, Glass Transition Temperatures, Volume Shrinkage, and Internal Pigmentability for Unsaturated Polyester, Vinyl Ester, and Epoxy Resins
指導教授： 黃延吉
Yan-Jyi Huang
口試委員: 陳崇賢
Chorng-Shyan Chern
邱文英
Wen-Yen Chiu
學位類別： 碩士
Master
系所名稱： 工程學院 - 化學工程系
Department of Chemical Engineering
論文出版年： 2010
畢業學年度： 98
語文別： 英文
論文頁數： 286
中文關鍵詞： 核殼型橡膠 、DSC 、FTIR 、MMT 、體積收縮 、玻璃轉移溫度
外文關鍵詞： core-shell rubber (CSR), low-profile additive
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    • 本文之目的，乃探討四種特用添加劑，分別為：(1)奈米級及次微米級核殼型橡膠(core-shell rubber)添加劑(2)無機矽膠/有機高分子核殼型顆粒及(3)矽烷改質蒙特納石黏土(montmorillonite clay，MMT)(4)Raft型CSR，其對苯乙烯/不飽和聚脂(或乙烯基酯)/特用添加劑三成份系統及環氧樹脂/硬化劑/特用添加劑三成份系統之之聚合固化動力、抗體積收縮特性及玻璃轉移溫度等之影響。實驗之結果，吾人將配合苯乙烯/乙烯基脂樹脂/特用添加劑三成份系統在未反應前之相容性，聚合固化後之反應轉化率等因素之整合性實驗測量結果加以解釋。

    The effects of nano-scale and submicron-scale core shell rubbers (CSR), inorganic silica gel/organic polymer core-shell particle (CSP), silane-treated montmorillonite clay (MPSi-MMT) and alkyl-ammonium treated montmorillonite clay (AMMT) as low-profile additives (LPA) on the cure kinetics, glass transition temperatures and volume shrinkage for styrene (ST)/unsaturated polyester (or vinyl ester)/additive ternary systems and epoxy/curing agent/additive ternary systems have been investigated.
    The reaction kinetics during the cure was measured by Differential Scanning Calorimetry (DSC) and Fourier Transform Infrared Spectrometry (FTIR). Based on the Takayanagi mechanical models, the glass transition temperature in each region of the cured samples for ST/UP (or VER)/additive ternary systems and epoxy/curing agent/additive ternary systems was measured by the Dynamic Mechanical Analysis (DMA). The volume shrinkage of the cured sample was also measured using the density method.
    (Keyword: core-shell rubber (CSR) ; low-profile additive (LPA) ; montmorillonite (MMT) ; unsaturated polyester (UP) ; vinyl ester resin (VER) ; epoxy resin；curing kinetics ; glass transition temperature ; volume shrinkage)

    ACKNOWLEDGEMENT………………………………………………………..i CONTENTS………………………………………………………………………ii LIST OF TABLES..……………………………………………………………...vii LIST OF FIGURES..…………………………………………………………......xi ABSTRACT……………………………………………………………………xxvi CHAPTER I .............................................................................................................1 CHAPTER II ............................................................................................................3 II.1 UP ..................................................................................................................3 II.2 Vinyl Ester Resins .........................................................................................5 II.3 Epoxy Resins (EPR) ......................................................................................6 II.4 Crosslinking Copolymerization of Styrene and Unsaturated Polyester ........8 II.5 Kinetics Model for Unsaturated Polyester Resins .......................................11 II.6 Curing of Unsaturated Polyester Resin .......................................................16 II.7 Curing of Low-Shrink Polyester Resins ......................................................17 II.8 Effects of Core-Shell Rubber Tougheners ...................................................18 II.9 Montmorillonite Clay ..................................................................................21 II.10 Glass Transition Temperature for St/UP/LPA Ternary Systems ...............25 II.11 RAFT Polymerization ................................................................................26 CHAPTER III ........................................................................................................28 III.1 Materials .....................................................................................................28 III.1.1 Unsaturated Polyester (UP) Resins ......................................................28 III.1.2 Epoxy Resins (EPR) ............................................................................29 iii III.1.3 Vinyl Ester Resins (VER) ....................................................................30 III.1.4 Core Shell Rubber (CSR) Additive .....................................................32 III.1.5 Core Shell Particle (CSP) Additive : Si-PMA .....................................32 III.1.6 Montmorillonite Clay (MMT) PK-805, Pai Kong Tech Nanotechnology Co. ...........................................................................33 III.1.7 Sodium Chloride (NaCl), ACROS ......................................................33 III.1.8 Silane coupling agent : A-174, OSI Specialties...................................34 III.1.9 Aminolauric acid (12-aminododecanoic acid), Sigma-Aldrich ...........34 III.1.10 Styrene, ACROS ...............................................................................34 III.1.11 4,4'-methylenedianiline / 4,4'-diaminodiphenylmethane (DDM), ACROS ...............................................................................................34 III.1.12 4,4’- diaminodyphenyl sulfone (DDS), ACROS ..............................35 III.1.13 Initiator : Tert-butyl peroxybenzoate (TBPB), ACROS ....................35 III.1.14 Dichloromethane, ACROS ................................................................35 III.2 Instrumentation ...........................................................................................36 III.2.1 Differential Scanning Calorimeter, DSC Q20 .....................................36 III.2.2 Fourier Transform Infrared Spectroscopy (FTIR) , Nicolet iS10 .......36 III.2.3 Dynamic Mechanical Analyzer, DMA 2980 .......................................36 III.2.4 Vacuum pump (G-50DA). ...................................................................36 III.2.5 Thermostated silicon oil bath...............................................................36 III.2.6 Vacuum oven .......................................................................................36 III.2.7 Aluminum mold ...................................................................................36 III.2.8 Aluminium plate, which has size of 50x50x2 mm3 .............................36 iv III.3 Procedure of Experiment ............................................................................36 III.3.1 Modification of MMT Clay .................................................................36 III.3.2 Sample Preparation for Cure Kinetics Study .......................................38 III.3.3 Cured Sample Preparation for Volume Shrinkage Study ....................38 III.3.4 Cured Sample Preparation for Glass Transition and WAXS Study ....40 III.3.5 Internal Pigmentability Sample Preparation ........................................42 III.3.6 Optical Microscope Sample Preparation .............................................43 III.3.7 Differential Scanning Calorimetry (DSC) Experiment .......................43 III.3.8 Fourier Transform Infrared Spectroscopy (FTIR) Experiment ..........45 III.3.9 Dynamic Mechanical Analysis (DMA) Experiment ...........................46 III.3.10 Characterization of MMT ..................................................................47 III.4 Experimental Calculation ...........................................................................50 III.4.1 Sample Composition Calculation ........................................................50 III.4.2 The Overall Reaction Rate and Total C=C Bonds Conversion Calculation by DSC Experiment ........................................................51 III.4.3 The Styrene, UP / VER and Total C=C Conversion Calculation by FTIR Experiment ................................................................................52 III.4.4 Volume Shrinkage Calculation of Cured Binary and Ternary Systems ............................................................................................................54 III.4.5 TGA Experiment Calculation ..............................................................54 III.4.6 Characterization of Silane-treated MMT by FTIR ..............................54 CHAPTER IV ........................................................................................................57 IV.1 Compatibility for St/UP (or VER)/Additive Uncured Ternary System and Epoxy/DDM (or DDS)/ Additive Uncured Ternary System .....................57 v IV.2 Microstructure Morphology of Cured Sample ...........................................63 IV.2.1 St/UP and St/VER Binary Systems .....................................................63 IV.2.2 St/UP/Silane-treated MMT Ternary System .......................................67 IV.3 DSC Reaction Kinetics Study ....................................................................72 IV.3.1 Comparison of Neat UP and Neat VER Systems ................................72 IV.3.2 St/UP(MA-PA-PG)/Silane-treated MMT Ternary System .................76 IV.3.3 St/VER/E7-15 Ternary System ...........................................................80 IV.4 Reaction Kinetics Study by FTIR ..............................................................84 IV.4.1 Calibration Curve ................................................................................84 IV.4.2 Styrene, Unsaturated Polyester and Total C=C bonds Conversion Calculation ..........................................................................................93 IV.5 Characterization of MMT by FTIR ............................................................98 IV.5.1 Silane-treated MMT ............................................................................98 IV.5.2 Alkyl-ammonium treated MMT (AMMT) ........................................109 IV.5.3 Grafting Reaction Mechanism for the Synthesis of Silane-treated MMT and Quantitative Analysis for the Grafting Efficiency Based on the Peaks at 916 cm-1 (Al2OH) and 844 cm-1 (AlMgOH)................115 IV.6 The Takayanagi Models ...........................................................................121 IV.7 Glass Transition Temperature by Dynamical Mechanical Analysis (DMA) ..................................................................................................................123 IV.7.1 St/UP Binary System .........................................................................123 IV.7.2 St/VER Binary System ......................................................................137 IV.7.3 Comparison of St/UP and St/VER Binary Systems ..........................149 IV.7.4 St/UP/MMT Ternary System ............................................................154 vi IV.7.5 St/VER/E7-15 Ternary System .........................................................184 IV.7.6 Epoxy/DDM Binary System .............................................................190 IV.7.7 Epoxy/DDM/E7-15 Ternary System .................................................199 IV.7.8 Epoxy/DDS Binary System ...............................................................205 IV.8 Volume Shrinkage ....................................................................................215 IV.8.1 St/UP and St/VER Binary Systems ...................................................215 IV.8.2 St/UP(MA-PG)/Silane-treated MMT Ternary System ......................218 IV.8.3 St/UP(MA-PG)/AMMT Ternary System ..........................................221 IV.8.4 St/VER/E7-15 Ternary System .........................................................225 IV.8.5 Epoxy/DDM/E7-15 Ternary System .................................................230 IV.9 Thermogravimetric Analysis (TGA) ........................................................235 IV.10 WAXS Measurement .............................................................................238 CHAPTER V…………………………………………………………………... 252 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