以作者查詢圖書館館藏

、以作者查詢臺灣博碩士

、以作者查詢全國書目

、勘誤回報

、線上人數：35

、訪客IP：3.145.84.198

姓名	周哲睿(Che-juei Chou)  查詢紙本館藏	畢業系所	化學工程與材料工程學系
論文名稱	雙醇鏈長對嵌段性 PU 結構及性質的影響 (The studies of diol chain length effect on the structure and properties of segmented PU)
相關論文	★ PU橡膠血液相容性之探討 ★ PU發泡體的結構與性質 ★ POLY IP發泡體結構與性質之探討 ★ 非極性式poly-ip based PU軟質段末端改質的影響 ★ 高韌性環氧樹脂底膠之開發 ★ 水性PU之流變性質研究 ★ 完全相分離PU之完整形態研究 ★ 含矽膠PU之合成與血液相容性研究 ★ 奈米級嵌段式PU之動態機械性質 與微結構型態研究 ★ Hydroxyl Terminated Polyisoprene(HTIP)陰離子型水性PU合成與性質研究 ★ 陰離子型水性PU/有機蒙特納土奈米複合材料之製備與分析 ★ 非極性式poly-ip based PU 之軟質段末端改質對形態的影響 ★ 硬質鏈段不規則性對PU奈米形態之影響(II) ★ 苦楝油對於水性PU膨潤效應的性質研究 ★ 硬質鏈段不規則性對PU奈米形態之影響 ★ 尼龍表面親疏水性之研究
檔案	[Endnote RIS 格式]    [Bibtex 格式]    [相關文章]   [文章引用]   [完整記錄]   [館藏目錄]   [檢視]  [下載] 本電子論文使用權限為同意立即開放。 已達開放權限電子全文僅授權使用者為學術研究之目的，進行個人非營利性質之檢索、閱讀、列印。 請遵守中華民國著作權法之相關規定，切勿任意重製、散佈、改作、轉貼、播送，以免觸法。
摘要(中)	嵌段式聚氨基甲酸酯(Segmented Polyurethane，SPU)是一種團聯共聚物，本身的結構可分為兩大部分，分別是由多元醇所組成的軟質鏈段，及由二異氰酸酯與鏈延長劑所構成的硬質鏈段，由於兩大部分皆具有化學結構數目眾多特性，再加上不同的化學組成又會使兩鏈段之間產生不同的微相變化，所以使其擁有多變的化性及物性優勢。 　　本實驗室過去的研究中，為了瞭解巨大基團(Bulky diol)對嵌段性PU的影響，所以便於合成過程中，導入自行合成出的巨大基團來進行一系列的硬質鏈段改質，並對其進行一系列的深入研究。但由於巨大基團於反應時，是藉由兩末端的羥基(-OH)與二異氰酸酯反應，故其本身亦是鏈延長劑的一種，所以當巨大基團導入於反應中時，不僅會造成硬質鏈段於排列上的立體障礙，亦會延伸硬質鏈段的長度，進而影響硬質鏈段的排列，故以此觀點作為新的出發點，進行一系列的實驗與分析。 　　本實驗在合成過程中採用六種沒有支鏈的線性鏈延長劑，分別是EDO (Ethylene glycol)、PDO (1,3-Propanediol)、BDO (1,4-Butanediol)、PeDO (1,5-Pentanediol)、ODO (1,8-Octanediol)與NDO (1,9-Nonanediol)，至於二異氰酸酯則是使用MDI (4,4-diphenylmethane diisocyanate)，而多元醇則選用近非極性的polyesters polyols (Priplast1838)。在聚合過程中，將各別導入上述不同長度的線性雙醇來進行對硬質鏈段的改質，合成出一系列具有不同硬質鏈段長度與不同硬質鏈段段含量的非極性PU彈性體，並利用FT-IR、DMA、拉力測試、TGA、與DSC，探討PU於不同長度鏈延長劑的影響下所造成之性質與結構變化。
摘要(英)	Segmented Polyurethane (SPU) is a kind of block copolymer , for the structure , we could separated into two parts . One is soft segment , build up by poliol ; the other is compose by diisocyanate and chain extender , called hard segment . Because both of these parts have the property of large number of chemical structures , the other hand , different chemical composition will make the difference result between the two segments of the micro-domain change , so it has advantages of many chemical and physical properties . 　　Previous studies in our laboratory , in order to find the effective on bulky diol to segmented PU . We add in bulky diol which merge by ourselves for the series modify and further studies of hard segment . The reaction process of bulky diol also reaction by both ends of hydroxyl (-OH) and diisocyanate , we could identified a kind of chain extender . At the time we add bulky diol in reaction , not only lead the steric hindrance of arrangement , but also extend the length of hard segment . For this reason , we plan a series experiments for analysis . 　　In this experiment , I used six kind of linear chain extenders without branched-chains follow : EDO (Ethylene glycol) , PDO (1,3-Propanediol) , BDO (1,4-Butanediol) , PeDO (1,5-Pentanediol) , ODO (1,8-Octanediol) and NDO (1,9-Nonanediol) . We selected MDI (4,4-diphenylmethane diisocyanate) and nearly nonpolar polyesters polyols (Priplast1838) for diisocyanate and polyol used . We will add the different length linear diol as above mentioned in polymerization process for modified hard segment , to produce a series nonpolar PU elastomer with different chain extender length and hard segment content . We also use FT-IR , DMA , tensile , TGA and DSC to study PU’s properties and structural changes under the effective of different length of chain extender .
關鍵字(中)	★ 鏈延長劑長度 ★ 嵌段式聚氨基甲酸酯 ★ 硬質鏈段重量百分比	關鍵字(英)	★ chain extender's length ★ hard segment's weight percentage ★ segmented polyurethane
論文目次	摘要-----------------------------------------I Abstract------------------------------------II 致謝---------------------------------------III 目錄----------------------------------------IV 圖目錄-------------------------------------VII 表目錄---------------------------------------X 第壹章、序論---------------------------------1 第貳章、文獻回顧-----------------------------3 　2-1 PU的組成物質---------------------------4 　　2-1-1 多元醇 (Polyol)--------------------4 　　2-1-2 鏈延長劑 (Chain extender)----------6 　　2-1-3 二異氰酸酯 (Diisocyanate)----------7 　　2-1-4 催化劑 (Catalyst)------------------9 　2-2 PU的結構與型態------------------------10 　2-3 PU的機械性質--------------------------10 　2-4 PU的熱性質----------------------------15 　　2-4-1 PU的硬質相玻璃轉化溫度(Tg,H)------15 　　2-4-2 硬質相於PU中之規則度--------------15 　　2-4-3 PU的軟質相玻璃轉化溫度(Tg,S)------17 第參章、實驗規劃----------------------------18 　3-1 實驗動機------------------------------18 　3-2 實驗流程------------------------------18 　3-3 實驗設計------------------------------19 　3-4 藥品介紹------------------------------19 　3-5 實驗操作流程--------------------------20 　　3-5-1 反應物前製處理--------------------20 　　3-5-2 PU的合成步驟----------------------21 　　3-5-3 製備PU薄膜試片--------------------24 　3-6 實驗設備及分析儀器--------------------24 　3-7 各分析儀器之操作條件------------------24 第肆章、結果分析與討論----------------------26 　4-1 化學性質鑑定--------------------------26 　　4-1-1 紅外線光譜分析--------------------26 　4-2 物理性質鑑定--------------------------33 　　4-2-1 動態機械性質分析------------------33 　　4-2-2 機械性質分析----------------------40 　　4-2-3 熱重損失分析----------------------50 　　4-2-4 熱性質分析------------------------51 第伍章、結論--------------------------------55 參考文獻------------------------------------57
參考文獻	[1]　B. Asli et al. ,“ Melt-blowing thermoplastic polyurethane and polyether -block-amide elastomers : Effect of processing conditions and crystallization on web properties .”, Polym. Eng. Sci. , 49(7) , 1340-1349 , 2009 [2]　B. Asli et al. ,“ Crystallization behavior of elastomeric block copolymers : thermoplastic polyurethane and polyether-block-amide .”, J. of Appl. Polym. Sci. , 111(3) , 1246-1256 , 2009 [3]　S. P. Lin et al. ,“ Volume shrinkages and mechanical properties of various fiber-reinforced hydroxyethyl methacrylate-polyurethane/unsaturated polyester composites .”, Composites Sci. and Technol. , 68(3-4) , 709-717 , 2008 [4]　M. N. S. Kumar and Siddaramaiah ,“ Thermo gravimetric analysis and morphological behavior of castor oil based polyurethane–polyester nonwoven fabric composites .” J. of Appl. Polym. Sci. , 106(5) , 3521-3528 , 2007 [5]　D. J. Hourston et al. ,“ Structure-property study of polyurethane anionomers based on various polyols and diisocyanates .”, J. of Appl. Polym. Sci. , 66(10) , 2035-2044 , 1997 [6]　R. A. Phillips et al. ,“ Structure-property relationships and moisture sensitivity of PDMS/PTMO mixed soft segment urethane elastomers .”, J. of Macromol. Sci. Phys. , 27(2-3) , 245-274 , 1988 [7]　X. H. Yu et al. ,“ Polydimethylsiloxane-polyurethane elastomers : Synthesis and properties of segmented copolymers and related zwitterionomers .”, J. of Polym. Sci. Polym. Phys.-Ed. , 23(11) , 2319-2338 , 1985 [8]　T. A. Speckhard et al. ,“ Properties of polyisobutylene polyurethane block copolymers : 2. Macroglycols produced by the ‘inifer’ technique .”, Polymer , 26(1) , 55-69 , 1985 [9]　D. B. Klinedinst et al. ,“ Structure–property behavior of segmented polyurethaneurea copolymers based on an ethylene–butylene soft segment .”, Polymer , 46(23) , 10191-10201 , 2005 [10]　T. K. Chen et al. ,“ Effects of number-average molecular weight of network chain on physical properties of cis-polybutadiene-containing polyurethane .”, Polym. Eng. Sci. , 32(2) , 115-121 , 1992 [11]　C. Li et al. ,“ Morphology of segmented polybutadiene-polyurethane elastomers .”, Macromol. , 21(8) , 2367-2375 , 1988 [12]　B. Bengtson et al. ,“ Thermal and mechanical properties of solution polymerized segmented polyurethanes with butadiene soft segments .”, Polymer , 26(6) , 895-900 , 1985 [13]　C. M. Brunette et al. ,“ Structural and mechanical properties of polybutadiene-containing polyurethanes .”, Polym. Eng. Sci. , 21(3) , 163-171 , 1981 [14]　N. S. Schneider and R. W. Matton ,“ Thermal transition behavior of polybutadiene containing polyurethanes .”, Polym. Eng. Sci. , 19(15) , 1122-1128 , 1979 [15]　K. Ono et al. ,“ Effects of number-average molecular weight of liquid Hydroxy-terminated polybutadiene on physical properties of the elastomers .”, J. of Appl. Polym. Sci. , 21(23) , 3223-3235 , 1977 [16]　G. N. Petrov and A. S. Lykin ,“ Synthesis of oligomers with reactive end groups and elastomers derived from them. Review .”, Polym. Sci. U.S.S.R. , 20(6) , 1351-1362 , 1977 [17]　P. W. Ryan ,“ Polyurethane based on hydroxyl-terminated polybutadienes .”, Brit. Polym. J. , 3(3) , 145-153 , 1971 [18]　T. A. Speckhard and S. L. Cooper ,“ Ultimate tensile properties of segmented polyurethane elastomers : factors leading to reduced properties for polyurethanes based on nonpolar soft segments .”, Rub. Chem. Technol. , 59(3) , 405-431 , 1986 [19]　C. Hepburn , Polyurethane Eastomers , Appl. Sci. , London , 1982 [20]　Oertel and Guenter Eds. , Polyurethane Handbook , Hanser Publisher. , New York , 1985 [21]　S. B. Clough and N. S. Schneider ,“ Structural studies on urethane elastomers .” , J. of Macromol. Sci.-Phys. , B2(4) , 553-566 , 1968 [22]　D. Nissen and R. A. Markovs ,“ Aromatic diamines as chain extenders in RIM urethane elastomers .” , J. of Elastomers and Platics , 15(2) , 96-112 , 1983 [23]　D. Tyagi et al. ,“ Morphology and properties of segmented polyurethane-urea copolymers prepared via t-alcohol "chain extension" .”, Polmer Preprints , 26(2) , 12 , 1985 [24]　C. S. Schollenberger and F. D. Stewart ,“ Thermoplastic urethane structure and ultraviolet stability .”, Advances in urethane Sci. and Technol. , 2 , 71-108 ,1973 [25]　R. R. Aitken and G. M. F. Jeffs ,“ Thermoplastic polyurethane elastomers based on aliphatic diisocyanates. Thermal transitions .”, Polymer , 18(2) , 197-198 , 1977 [26]　J. W. Britain and P. G. Gemeinhardt ,“ Catalysis of the isocyanate-hydroxyl reaction .”, J. of Appl. Polym. Sci. , 4 , 207-211 , 1960 [27]　M. Serrano et al. ,“ Transport-morphology relationships in segmented polybutadiene polyurethanes : 1. Experimental results .”, Polymer , 28(10) , 1667-1673 , 1987 [28]　M. Serrano et al. ,“ Transport-morphology relationships in segmented polybutadiene polyurethanes : 2. Analysis .”, Polymer , 28(10) , 1674-1679 , 1987 [29]　D. J. Meier ,“ Theory of the morphology of block copolymers .”, Polym. Prepr. Am. Chem. Soc. Div. Polym. Chem. , 11(2) , 400-405 , 1970 [30]　C. Li and S. L. Cooper ,“ Direct observation of the micromorphology of polyether polyurethanes using high-voltage electron microscopy .”, Polymer , 31(1) , 3-7 , 1990 [31]　D. J. Kinning et al. ,“ Effect of morphology on the transport of gases in block copolymers .”, Macromol. , 20(5) , 1129-1133 , 1987 [32]　J. Blackwell and K. H. Gardner ,“ Structure of the hard segments in polyurethane elastomers .”, Polymer , 20(1) , 13-17 , 1979 [33]　J. Blackwell et al. ,“ Structure of polyurethane elastomers. X-ray diffraction and conformational analysis of MDI-propandiol and MDI-ethylene glycol hard segments .”, Polymer , 22(11) , 1534-1539 , 1981 [34]　R. Bonart ,“ Thermoplastic elastomers .”, Polymer , 20(11) , 1389-1403 , 1979 [35]　J. Blackwell and M. R. Nagarajan ,“ Conformational analysis of poly(MDI-butandiol) hard segment in polyurethane elastomers .”, Polymer , 22(2) , 202-208 , 1981 [36]　M. Xu et al. ,“ Structure and morphology of segmented polyurethanes. 1. Influence of incompatability on hard-segment sequence length .”, Polymer , 24(10) , 1327-1332 , 1983 [37]　T. A. Speckhard et al. ,“ Properties of polyisobutylene-polyurethane block copolymers. I. Macroglycols from ozonolysis of isobutylene-isoprene copolymer .”, Polym. Eng. Sci. , 23(6) , 337-349 , 1983 [38]　T. L. Smith ,“ Tensile strength of polyurethane and other elastomeric block copolymers .”, J. of Polym. Sci. Polym. Phys.-Ed. , 12(9) , 1825-1848 , 1974 [39]　T. L. Smith ,“ Strength of elastorners — a perspective .”, Polym. Eng. Sci. , 17(3) , 129-143 , 1977 [40]　R. Bonart and K. Hoffmann ,“ Orientational behavior of segmented polyether urethanes as a function of strain and solvents used .”, Macromol. Chem. Phys. , 184(7) , 1529-1546 , 1983 [41]　J. T. Koberstein et al. ,“ Compression-molded polyurethane block copolymers. 1. Microdomain morphology and thermomechanical properties .”, Macromol. , 25(23) , 6195-6204 , 1992 [42]　J. T. Koberstein and L. M. Leung ,“ Compression-molded polyurethane block copolymers. 2. Evaluation of microphase compositions .”, Macromol. , 25(23) , 6205-6213 , 1992 [43]　邱家永，「嵌段式PU的結構與性質(I)」，國立中央大學，博士論文，民國86年 [44]　C. Z. Yang et al. ,“ Morphology and properties of polybutadiene- and polyether-polyurethane zwitterionomers .”, Macromol. Chem. , 184(3) , 651-668 , 1983 [45]　T. A. Speckhard et al. ,“ Properties of segmented polyurethane zwitterionomer elastomers .”, J. of Macromol. Sci.-Phys. , B23(2) , 175-199 , 1984 [46]　Y. Camberlin et al. ,“ Model hard segments from diphenylmethane diisocyanate and different chain extenders, and corresponding linear block polyurethanes .”, J. of Polym. Sci. Polym. Phys.-Ed. , 20(6) , 1445-1456 , 1982 [47]　I. Yilgor et al. ,“ Siloxane-urea segmented copolymers. 1. Synthesis and characterization of model polymers from MDI and α,ω-bis(aminopropyl)polydimethylsiloxane .”, Polym. Bull. , 8(11-12) , 535-542 , 1982 [48]　Y. Camberlin et al. ,“ Synthesis and DSC study of model hard segments from diphenylmethane diisocyanate and butane diol .”, J. of Polym. Sci. Polym. Chem. Ed. , 20(2) , 383-392 , 1982 [49]　Y. Li et al. ,“ Multiphase structure of a segmented polyurethane: effects of temperature and annealing .”, Macromol. , 25(26) , 7365-7372 , 1992 [50]　P. W. Seymour and S. L. Cooper ,“ Thermal Analysis of Polyurethane Block Polymers .”, Macromol. , 6(1) , 48-53 , 1973 [51]　T. R. Hesketh et al. ,“ Differential scanning calorimetry analysis of morphological changes in segmented elastomers .”, Polym. Eng. Sci. , 20(3) , 190-197 , 1980 [52]　L. M. Leung and J. T. Koberstein ,“ DSC annealing study of microphase separation and multiple endothermic behavior in polyether-based polyurethane block copolymers .”, Macromol. , 19(3) , 706-713 , 1986 [53]　J. T. Koberstein and T. P. Russell ,“ Simultaneous SAXS-DSC study of multiple endothermic behavior in polyether-based polyurethane block copolymers .”, Macromol. , 19(3) , 714-720 , 1986 [54]　Y. Li et al. ,“ Multiphase structure of segmented polyurethanes: its relation with spherulite structure .”, J. of Polym. Sci. Polym. Phys.-Ed. , 31(7) , 853-867 , 1993 [55]　謝添壽，「嵌段式PU的結構與性質(II)」，國立中央大學，博士論文，民國87年 [56]　Z. S. Petrovic et al. ,“ The effect of soft-segment length and concentration on phase separation in segmented polyurethanes .”, J. of Polym. Sci. Polym. Phys.-Ed. , 27(3) , 545-560 , 1989 [57]　J. W. C. Van Bogart et al. ,“ Structure-property relationships in polycaprolactone-polyurethanes .”, J. of Polym. Sci. Polym. Phys.-Ed. , 21(1) , 65-95 , 1983 [58]　S. C. S. Paik et al. ,“ Properties of segmented poly(urethaneureas) based on 2,4-toluene diisocyanate. 1. Thermal transitions, x-ray studies, and comparison with segmented poly(urethanes) .”, Macromol. , 13(1) , 111-116 , 1980 [59]　N. S. Schneider et al. ,“ Structure and properties of polybutadiene-containing polyurethanes .”, Advance in Urethane Sci. and Technol. , 8 , 49-74 , 1981 [60]　C. P. Christenson et al. ,“ Model MDI/butanediol polyurethanes : molecular structure, morphology, physical and mechanical properties .”, J. Polym. Sci. Polym. Phys. , 24(7) , 1401-39 , 1986 [61]　M. Minsheng et al. ,“ Studies on cure reaction kinetics of diisocyanates and hydroxyl terminated polybutadiene by IR .”, 高分子材料科學與工程 , 1993(02) , 9:65 , 1993 [62]　C. Zhang et al. ,“ Amide II and amide III bands in polyurethane model soft and hard segments .”, Polym. Bull. , 60(1) , 97-101 , 2008 [63]　J. Lin et al. ,“ Preparation and characterization of waterborne polyurethaneurea composed of dimer fatty acid polyester polyol .”, Journal of Nanomaterials , 2006(1) , 1-10 , 2006 [64]　Y. Ren et al. ,“ Synthesis of polyurethane acrylates by hydrogenated castor oil and dimer-based polyester diol and study on pressure-sensitive adhesive .”, J. of Appl. Polym. Sci. , 98(4) , 1814-1821 , 2005 [65]　Y. Ren et al. ,“ Synthesis of polyurethane acrylate and application to ultraviolet-curable pressure-sensitive adhesive .”, Polymer-Plastics Technol. and Eng. , 45(4) , 495-502 , 2006 [66]　廖家陽，「巨大基團對Polyurethane urea結構與性質的影響」，國立中央大學，碩士論文，民國96年 [67]　李國銘，「硬質鏈上巨大基團對防水性polyester PU的影響」，國立中央大學，碩士論文，民國99年 [68]　李俊德，「軟質段分子量及硬質段鏈延長劑對PB-based PU 之影響」，國立中央大學，碩士論文，民國83年 [69]　J. Blackwell et al. ,“ Structure of polyurethane elastomers : effect of chain extender length on the structure of MDI/diol hard segments .”, Macromol. Sci. , 23(7) , 950-956 , 1982 [70]　Y. Camberlin and J. P. Pascault ,“ Quantitative DSC evaluation of phase segregation rate in linear segmented polyurethanes and polyurethaneureas .”, J. of Polym. Sci. Polym. Phys.-Ed. , 21(2) , 415-423 , 1983 [71]　A. Takahara et al. ,“ Microphase separated structure and blood compatibility of segmented poly(urethaneureas) with different diamines in the hard segment .”, Polymer , 26(7) , 978-986 , 1985 [72]　J. Blackwell and C. D. Lee ,“ Hard-segment polymorphism in MDI/diol-based polyurethane elastomers .”, J. of Polym. Sci. Polym. Phys. Ed. , 22(4) , 759-772 , 1984 [73]　黃世敏，「非極性式水性聚胺基甲酸酯－?酯之合成、結構與物性」，國立中央大學，博士論文，民國97年 [74]　高世濱，「巨大基團對Polyurethane結構與性質的影響」，國立中央大學，碩士論文，民國98年 [75]　J. W. C. Van Bogart et al. ,“ Annealing-induced morphological changes in segmented elastomers .”, Polymer , 22(10) , 1428-1438 , 1981
指導教授	陳登科(Teng-ko Chen)	審核日期	2011-7-8
推文	facebook   plurk   twitter   funp   google   live   udn   HD   myshare   reddit   netvibes   friend   youpush   delicious   baidu
網路書籤	Google bookmarks   del.icio.us   hemidemi   myshare