Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/3814
DC FieldValueLanguage
dc.contributor鄭如忠zh_TW
dc.contributor林慶炫zh_TW
dc.contributor陳幹男zh_TW
dc.contributor蔣見超zh_TW
dc.contributor.advisor戴憲弘zh_TW
dc.contributor.advisorShenghong A. Daien_US
dc.contributor.author林信佑zh_TW
dc.contributor.authorLin, Hsing-Yoen_US
dc.contributor.other中興大學zh_TW
dc.date2011zh_TW
dc.date.accessioned2014-06-06T05:32:50Z-
dc.date.available2014-06-06T05:32:50Z-
dc.identifierU0005-1708201018033000zh_TW
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H.; Tiefenthal, H. E.; Lokken, R. J.; Nickels, J. E.; Atwood, G. R.; Pavlik, F. J. J. Org. Chem. 1958, 23 (4), 544-549. 74 Dai, Shenghong A. US Patent 4720584, 1988. 75 Williamson, A. W. J. Chem. Soc. 1852, 4, 229. 76 Imai, Y.; Abe, S.; Ueda, M. J. Polym. Sci., Polym. Chem. Ed. 1981, 19, 3285-3291. 77 Lindley, J. Tetrahedron 1984, 40, 1433-1456. 78 Theil, F. Angew. Chem. Int. Ed. 1999, 38, 2345-2347. 79 Weingarten, H. J. Org. Chem. 1964, 29, 977-978. 80 Wang, J.; Shao, J.; Ren, G. Huaxue Shiji 1994, 16 (6), 371-372. 81 Johnson, G. W. GB 810069, 1959. 82 Wang, S.; Wang, J.; Liu, T.; Mo, Z.; Zhang, H.; Yang, D.; Wu, Z. Macromol. Chem. Phys. 1997, 198, 969-982. 83 Haddleton, David M.; Sahota, Hardeep S.; Taylor, Paul C.; Yeates, Stephen G. J. Chem. Soc., Perkin Trans. 1, 1996, 649-656. 84 Schuur, M.; Feijen, J.; Gaymans, Reinoud J. Polymer 2005, 46,4584-4595. 85 Washio, I.; Shibasaki, Y.; Ueda, M. Macromolecules 2005, 38, 2237-2246. 86 Kuo, M.-J.; Jeng, R.-J.; Su, W.-C.; Dai, Shenghong A. Macromolecules 2008, 41, 682-690. 87 Complete name of 23a is 4-methyl-2,4-bis(p-hydroxyphenyl)-pent-1-ene and 23b-c are 4-methyl-2,4-bis(p-hydroxyphenyl)-pent-2-enes (Webb, R. F.; Hinton, I. G. US Patent 3264358, 1966). 88 Complete name of 24 is 1-(4-hydroylphenyl)-1,3,3-trimethyl indan-6-ol (Farnham, A. G. US Patent 3288864, 1966). 89 Complete name of 25 is 6,6en_US
dc.identifier.urihttp://hdl.handle.net/11455/3814-
dc.description.abstractIn this research, we utilized bisphenol A (BPA), a low-cost commodity product, as the common starting material to develop new synthetic schemes for preparation of difunctional speciality intermediates for performance polymers, such as alkoxylated ether diols, isopropylidene bis-phenylene di-alkyl biscarbamates, 2,2-bis(4-isocyanatophenyl)propane, 2,2-bis(4-aminophenyl) propane, indane-ring bisphenols and dual functional hydroquinones. Some of them have been demonstrated in the synthesis of specialty polymers. First of all, a one-pot epoxide-free alkoxylation process has been developed for phenolic compounds particularly for diols of BPA. The process involves heating phenolic compounds and urea in 1,2-glycols using Na2CO3/ZnO as co-catalysts. This process is particularly well-suited for making short chain-length alkoxyether alcohols of phenols. For instance, BPA was converted into their respective mono-alkoxylated ether alcohols on each of their phenolic groups in 80-95% isolated yields. In propoxylation of phenols, this approach shows great product selectivity favoring production of high secondary alcohols over primary alcohols in isomeric ratios of nearing 95/5. Since ammonia and carbon dioxide could be recycled back to urea for re-use, this alkoxylation can be regarded simply as a condensation reaction between phenols and 1,2-glycols giving off water as the only overall by-product. This one-pot process is simple, safe and environmentally friendlier than the conventional alkoxylated processes based on ethylene oxide (EO) or propylene oxide (PO). Secondly, through the experiments on BPA's cleavage by an acid-catalyzed condition, it was found that 4-IPP carbocation can be readily generated by addition of BPA in concentrated sulfuric acid at ambient temperature so that it shows the facility and stability of the IPP carbocation in the acid-cleavage of BPA. For an extended utilization of the carbocation's mechanism, a trans-alkylation reaction has been developed for rapid synthesis of isopropylidene bis-phenylene biscarbamate 12 by adding mono-carbamates in the first step and followed by removal of the replaced phenol under reduced pressure. By this simple process, biscarbamate 12a with isopropylidene bis-phenylene structure can be prepared in about 80% yields. Furthermore, the biscarbamate was utilized as the precursor to prepare diisocyanate 13a and dianiline 14a by thermolysis and hydrolysis, respectively. In addition, these isopropylidene bis-phenylene intermediates could be served as the raw materials to carry out a non-phosgene route to prepare isocyanate or relative polymers. Moreover, it was found that the stable 4-IPP carbocation could be also used for facile synthesis of 4-IPP, 4-IPP dimers, or indane-ring bisphenol derivatives specifically by choosing acid media of different acid-strength. Lastly, we have carried out a three-step synthetic approach of using 4-IPP as the raw material for preparation of dual functional hydroquinone intermediates in the following three sequential steps: (1) functionalization of the hydroxyl group of IPP first, (2) oxidation of isopropenyl group of IPP derivatives from the first step with hydrogen peroxide, and (3) functionalization of the new hydroxyl group with another derivative from step two. This general strategy is new and can make varieties of hydroquinone derivatives in precision for the first time. Due to the reactivity differences between two functional groups, the synthesized hydroquinone intermediates are particular attractive for the use in iterative or prepolymer synthesis In summary, in this research, it was found that BPA could be utilized as an important raw material for synthesizing polymer intermediates especially those with isopropylidene bis-phenylene and hydroquinone skeletons which are not readily accessible by any known synthetic methodologies.en_US
dc.description.tableofcontentsAbstract .................................................................................................................i List of Tables ........................................................................................................v List of Figures .....................................................................................................vi List of Schemes .................................................................................................viii 1. Introduction ....................................................................................................1 2. One-Pot Alkoxylation of Phenols Using Urea with 1,2-Glycols .................4 2.1 Literature Review........................................................................................4 2.2 Experiments.................................................................................................9 2.3 Results and Discussion..............................................................................11 2.3.1 General one-pot ethoxylation condition.........................................11 2.3.2 Mechanism: IR monitoring, by-product formations and optimization....................................................................................12 2.3.3 Product selectivity in propoxylation with urea and 1,2-propylene glycol..............................................................................................15 2.3.4 Catalysts used in urea-glycol alkoxylation.....................................17 2.3.5 Higher alkoxylation of phenols with EG/PG-urea alkoxylation....18 2.3.6 Competitive reaction between in EG/PG-urea alkoxylation..........19 2.3.7 Green chemistry implication..........................................................19 3. Synthesis of Isopropylidene Bis-Phenylene Containing Polymer Intermediates ................................................................................................21 3.1 Literature Review......................................................................................21 3.2 Experiments..............................................................................................26 3.3 Results and Discussion.............................................................................32 3.3.1 Acid medium used in trans-alkylation reaction.............................32 3.3.2 Synthesis of 2,2-bis(4-isocyanatophenyl)propane (DM-MDI) and its application in polyurethanes......................................................35 3.3.3 Synthesis of 2,2-bis(4-aminophenyl)propane and it application in polyureas........................................................................................38 3.3.4 Other species used in trans-alkylation reaction..............................41 4. Preparation of 4-Isopropenyl Phenol (4-IPP) and Used as a Dual Functional Group Intermediate for Further Synthesis ............................42 4.1 Literature Review......................................................................................42 4.2 Experiments..............................................................................................48 4.3 Results and Discussion..............................................................................52 4.3.1 Generation of stable 4-IPP carbocation and preparation of 4-IPP dimers from BPA............................................................................52 4.3.2 Synthesis of indane-ring bisphenols...............................................55 4.3.3 Synthesis of hydroquinone dual functional intermediates..............58 5. Conclusion .....................................................................................................62 6. Appendix .......................................................................................................65 References and Notes .........................................................................................76en_US
dc.language.isoen_USzh_TW
dc.publisher化學工程學系所zh_TW
dc.relation.urihttp://www.airitilibrary.com/Publication/alDetailedMesh1?DocID=U0005-1708201018033000en_US
dc.subject雙酚Azh_TW
dc.subjectbisphenol Aen_US
dc.subject尿素法烷烯醚化zh_TW
dc.subject烷交換反應zh_TW
dc.subject非光氣法zh_TW
dc.subject碳陽離子zh_TW
dc.subject4-異丙烯基酚zh_TW
dc.subject異質雙官能基對苯二酚zh_TW
dc.subjecturea-glycol alkoxylationen_US
dc.subjecttrans-alkylationen_US
dc.subjectisopropylidene bis-phenyleneen_US
dc.subjectnon-phosgeneen_US
dc.subjectcarbocationen_US
dc.subject4-IPP dimersen_US
dc.subject4-isopropenyl phenolen_US
dc.subjectdual-functional hydroquinonesen_US
dc.title用雙酚A作為起始原料以合成高分子中間體zh_TW
dc.titleSynthesis of Polymer Intermediates Using Bisphenol A as the Starting Materialen_US
dc.typeThesis and Dissertationzh_TW
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