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Author : Youngjoon Lee
Publisher :
ISBN 13 :
Total Pages : 372 pages
Book Rating : 4.:/5 (453 download)
Download or read book Anionic Synthesis of Functionalized Polymers Using Functionalized Organolithium Initiators written by Youngjoon Lee and published by . This book was released on 2000 with total page 372 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Author : Sung Hoon Jang
Publisher :
ISBN 13 :
Total Pages : 602 pages
Book Rating : 4.:/5 (385 download)
Download or read book Anionic Synthesis of Functionalized Polymers Using Functionalized Organolithium Initiators written by Sung Hoon Jang and published by . This book was released on 1997 with total page 602 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Author : Jonathan E. Janoski
Publisher :
ISBN 13 :
Total Pages : 160 pages
Book Rating : 4.:/5 (912 download)
Download or read book Anionic Synthesis of Functionalized Polymers written by Jonathan E. Janoski and published by . This book was released on 2010 with total page 160 pages. Available in PDF, EPUB and Kindle. Book excerpt: The synthesis of well-defined functionalized polymers is an important area of research due to their wide array of applications. The work presented herein can be divided into three categories: a) functional initiator synthesis; b) chain-end and in-chain functionalization and c) functional monomer synthesis and polymerization. All three methods involve both anionic polymerization and hydrosilation. In this work, all anionic polymerizations were performed at room temperature in hydrocarbon solvent with an alkyllithium initiator. A functional 4-pentenyllithium initiator was prepared in 70% yield and was used for the synthesis of [alpha] and [alpha,omega]-functionalized polystyrene. 4-Pentenyllithium was used to initiate styrene polymerization in benzene in the presence of 5 equivalents of tetrahydrofuran. Narrow polydispersity indices and good agreement between calculated and observed molecular weights were observed for the methanol-terminated product. [alpha]-Triethoxysilyl-functionalized polystyrene was quantitatively prepared by hydrosilation with triethoxysilane and [alpha]-4-pentenylpolystyrene. [alpha]-4-Pentenyl-[omega]-silyl hydridefunctionalized polystyrene and [alpha]-4-pentenyl-[omega]-thiol hydride functionalized polystyrene were quantitatively prepared by terminating [alpha]-4-pentenylpoly(styryl)lithium with chlorodimethylsilane and ethylene sulfide, respectively. The [alpha]-4-pentenyl-[omega]-silyl hydride-functionalized polystyrene showed good agreement between calculated and observed molecular weights and a narrow polydispersity. [alpha]-4-Pentenyl-[omega]-thiolfunctionalized polystyrene showed a dimer peak due to oxidative coupling when quenched with methanol. Triethoxysilyl-functionalized, high-1,4-polybutadiene was prepared by reacting the pendant double bonds of the 1,2-units with triethoxysilane via hydrosilation. High-yielding reactions between the polymeric organolithium chain-ends and silyl chlorides were used to obtain the desired polymeric silyl hydrides for further functionalization. In-chain and chain-end cyano-functionalized polystyrenes were prepared. Chain-end, silyl hydride-functionalized polystyrene was prepared quantitatively. Hydrosilation of chain-end, silyl hydride-functionalized polystyrene with allyl cyanide resulted in [omega]-cyano-functionalized polystyrene, which was prepared in 87% yield. In-chain, silyl hydride-functionalized polystyrene was prepared by terminating excess poly(styryl)lithium with dichloromethylsilane. The remaining poly(styryl)lithium was terminated with ethylene oxide to aid in chromatographic separation to yield the pure in-chain, silyl hydride-functionalized polystyrene in 96% yield. Hydrosilation of in-chain, silyl hydride-functionalized polystyrene with allyl cyanide resulted in cyano in-chain functionalized polystyrene in 58% yield after 2 weeks of reaction time at elevated temperature. [omega]-Silyl dihydride-functionalized polystyrene was prepared in 92% yield by inverse addition of poly(styryl)lithium to dichloromethylsilane then reduction with lithium aluminum hydride. Functionalization with allyl cyanide yielded [omega]-dicyanofunctionalized polystyrene quantitatively. Synthesis of functionalized polymers from silyl hydride-substituted monomers was also investigated. para-Dimethylsilylstyrene was prepared from 4-chlorostyrene in 84% yield. Homopolymerization, copolymerization, and end-capping of poly(styryl)lithium in cyclohexane with this monomer was investigated, and it was found that a linking reaction is occuring. meta-Dimethylsilylstyrene was prepared from 3-bromostyrene in 75% yield. Anionic homopolymerization, and copolymerization of this monomer were investigated, and it was found that a more vigorous linking reaction was taking place compared to the para-substituted analog.
Author : Michael Olechnowicz
Publisher :
ISBN 13 :
Total Pages : 196 pages
Book Rating : 4.:/5 (294 download)
Download or read book Synthesis of End-chain and In-chain Functionalized Polymers by Anionic Polymerization written by Michael Olechnowicz and published by . This book was released on 2008 with total page 196 pages. Available in PDF, EPUB and Kindle. Book excerpt: "The synthesis of homopolymers and block copolymers containing metal coordinating ligands is an important area of research due to the potential applications of these polymers in the fields of optics, electronics, and photonics. Specifically, the terpyridine group is very useful, since it can act as a tridentate chelating ligand due to its strategically positioned, three nitrogen atoms. This allows it to form strong complexes with a variety of transition metal ions. The hydroxyl functionality is another important group due to numerous applications of well-defined hydroxyl-functionalized polymers. They can react with other functional groups on other polymers for chain extension, branching, or crosslinking. They can also be used as macroinitiators for the polymerization of other monomers such as lactide and lactone. Alkyllithium-initiated, living anionic polymerization offers excellent control over molecular weight and molecular weight distribution. The absence of termination and chain transfer steps makes these systems ideally suited for the preparation of chain-end functionalized polymers by the reaction of the living chain ends with appropriate monomers or terminating agents. A recently reported general anionic functionalization method was used to create well-defined terpyridine and hydroxyl end-functionalized polymers. In the first step, living polymeric organolithium compounds were reacted with silyl chlorides to form the corresponding silyl hydride-functionalized polymers. Then, these polymers were reacted with substituted alkenes in the presence of a hydrosilation catalyst to form the corresponding functionalized polymers. A new method was also developed, based on similar chemistry, to prepare an in-chain functionalized diblock copolymer where a variety of functional groups can be placed directly at the interface of the two blocks. This method was used to prepare both in-chain hydroxyl- and terpyridine-functionalized polystyrene-b-polyisoprene copolymers. Lewis bases effect dramatic changes in microstructure, initiation rates, propagation rates and monomer reactivity ratios for alkyllithium-initiated polymerizations of vinyl monomers in hydrocarbon solution. The stability of polymeric organolithium compounds and the mechanism of decomposition in the presence of various stoichiometric equivalents of tetrahydrofuran in benzene solutions were studied due the importance of THF as an additive."--Abstract.
Author : Manuela Ocampo
Publisher :
ISBN 13 :
Total Pages : 210 pages
Book Rating : 4.:/5 (911 download)
Download or read book Anionic Synthesis of Well-defined Functionalized and Star-branched Polymers written by Manuela Ocampo and published by . This book was released on 2007 with total page 210 pages. Available in PDF, EPUB and Kindle. Book excerpt: Novel methods for the synthesis of chain-end and in-chain functionalized polymers, as well as star polymers, were developed using anionic polymerization techniques. A new mechanism for the reaction of polymeric organolithium compounds with thiiranes has been found. The reaction of poly(styryl)lithium and poly(butadienyl)lithium with propylene sulfide and ethylene sulfide was investigated in hydrocarbon solution for the preparation of thiol-functional polymers. It was found by MALDI-TOF mass spectral analysis of the reaction products that the reaction proceeded by attack of the anion on the methylene carbon atom of the thiirane ring followed by ring opening to form the thiol-functionalized polymer. The reaction of poly(styryl)lithium with trimethylene sulfide did not produce the corresponding thiol-functionalized polymer; the resulting methyl-terminated polymer was formed by attack of the anion on the sulfur atom followed by ring opening to form a primary carbanion. A new method for synthesis of alkoxysilyl-functionalized polymers was developed. Using a general functionalization methodology based on the hydrosilation of vinyltrimethoxysilane with [omega]-silyl hydride-functionalized polystyrene, alkoxysilyl-functionalized polystyrene was obtained in high yield (83 %). The main side product was vinylsilane-functionalized polymer. A small amount of dimer (approximately 2 %) was formed from the hydrosilation reaction of silyl hydride-functionalized polymer and vinylsilane-functionalized polymer. Star polymers with an average number of 6.8 arms were obtained by reacting poly(styryl)lithium with 6.6 equivalents of vinyldimethylchlorosilane in benzene at 30 °C. It was found that, in benzene at 30 °C, vinyldimethylchlorosilane is an efficient linking agent for the preparation of well-defined star-branched polymers. In contrast, the reaction of poly(styryl)lithium with 5 equivalents of vinyldimethylchlorosilane in THF at -78 °C produced vinylsilane-functionalized polymer in high yield (> 93 %). Poly(styryl)lithium was reacted with 2.5 equivalents of vinyldimethylethoxysilane; reaction occurred exclusively by the addition of the living anion to the vinyl group. In-chain, dihydroxyl-functionalized polystyrene was prepared by reaction of poly(styryl)lithium and 1,3-butadiene diepoxide. The hydroxyl functionalities were activated with potassium naphthalenide. Addition of ethylene oxide monomer yielded the corresponding heteroarm polystyrene/poly(ethylene oxide) stars. Two commercially available triepoxides, N,N-diglycidyl-4-glycidyloxyaniline and Tactix 742, were used to prepare the corresponding 3-armed stars in high yield.
Author : Henry Hsieh
Publisher : CRC Press
ISBN 13 : 9780824795238
Total Pages : 748 pages
Book Rating : 4.7/5 (952 download)
Download or read book Anionic Polymerization written by Henry Hsieh and published by CRC Press. This book was released on 1996-03-15 with total page 748 pages. Available in PDF, EPUB and Kindle. Book excerpt: This work introduces the basic theories and experimental methods of anionic polymerization as well as the synthesis, analysis and characteristics of anionic polymerized products. It details the creation of linear and branched polymers, random and block copolymers, graft and macromonomers, and many other substances. The work emphasizes the relationship between fundamental principles and commercial applications.;College or university bookstores may purchase five or more copies at a special student price, available on request from Marcel Dekker, Inc.
Author : Norazilawati Muhamad Sarih
Publisher :
ISBN 13 :
Total Pages : 0 pages
Book Rating : 4.:/5 (969 download)
Download or read book Synthesis of Well-defined Multi-end Functionalized Polymers Via Living Anionic Polymerization written by Norazilawati Muhamad Sarih and published by . This book was released on 2010 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Author : Maurice Morton
Publisher : Elsevier
ISBN 13 : 0323158846
Total Pages : 257 pages
Book Rating : 4.3/5 (231 download)
Download or read book Anionic Polymerization: Principles and Practice written by Maurice Morton and published by Elsevier. This book was released on 2012-12-02 with total page 257 pages. Available in PDF, EPUB and Kindle. Book excerpt: Anionic Polymerization: Principles and Practice describes the unique nature of the anionic mechanism of polymerization. This book is composed of two parts encompassing 11 chapters that cover the aspects of the synthetic possibilities inherent in this system. Part I deals with the various aspects of anionic polymerization mechanism, including the monomers, initiators, solvents, and the involved initiation and propagation reactions. This part also describes the copolymerization and organolithium polymerization reactions of styrene and dienes. Part II explores the applications of anionic polymerization in polymer synthesis. This part specifically tackles the synthesis of narrow molecular weight, branched and a,?-difunctional polymers, and block copolymers. Polymer chemists and researchers who work in the chemical industry and who would wish to utilize the unique features of anionic polymerization in the synthesis of new products will find this book invaluable.
Author : Huimin Yang
Publisher :
ISBN 13 :
Total Pages : 400 pages
Book Rating : 4.:/5 (378 download)
Download or read book Anionic Synthesis of Functionalized Linear and Star-branched Polymers written by Huimin Yang and published by . This book was released on 1997 with total page 400 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Author : Sumana Roy Chowdhury
Publisher :
ISBN 13 :
Total Pages : 192 pages
Book Rating : 4.:/5 (225 download)
Download or read book Anionic Synthesis of In-chain and Chain-end Functionalized Polymers written by Sumana Roy Chowdhury and published by . This book was released on 2006 with total page 192 pages. Available in PDF, EPUB and Kindle. Book excerpt: "The objective of this work was to anionically synthesize well-defined polymers having functional groups either at the chain-end or along the polymer chain. General functionalization methods (GFM) were used for synthesizing both kinds of polymers. Chain-end functionalized polymers were synthesized by terminating the anionically synthesized, living polymer chains using chlorodimethylsilane. Hydrosilation reactions were then done between the silyl-hydride groups at the chain-ends and the double bonds of commercially available substituted alkenes. This produced a range of well-defined polymers having the desired functional groups at the chain ends. In-chain functionalized polymers were synthesized by anionically polymerizing a silyl-hydride functionalized styrene monomer: (4-vinylphenyl)dimethylsilane. Polymerizations were done at room temperature in hydrocarbon solvents to produce well-defined polymers. Functional groups were then introduced into the polymer chains by use of hydrosilation reactions done post-polymerization. The functionalized polymers produced were characterized using SEC, 1H and 13C NMR, FTIR, MALDI TOF mass spectrometry and DSC. The monomer reactivity ratios in the copolymerization of styrene with (4-vinylphenyl)dimethylsilane were also measured. A series of copolymerizations was done with different molar ratios of styrene(S) and (4-vinylphenyl)dimethylsilane(Si). Three different methods were used to determine the values of the monomer reactivity ratios: Fineman-Ross, Kelen-Tudos and Error-In-Variable (EVM) methods. The average values of the two monomer reactivity ratios obtained were: r(Si) =0.16 and r(S) = 1.74. From these values it was observed that in the copolymerization of styrene with (4-vinylphenyl)dimethylsilane, the second monomer was preferentially incorporated into the polymer chain. Also, r(Si)r(S) = 0.27, which shows that the copolymer has a tendency to have an alternating structure. Amino acid-functionalized polymers (biohybrids) were synthesized by using a simple and efficient, three-step method. The first step was to make a copolymer of styrene with (4-vinylphenyl)dimethylsilane, followed by introduction of amine functional groups into the polymer chain, suing a hydrosilation reactions between the silyl-hydride units in the copolymer chain and the double bond of allyl amine. The third step was a condensation reaction between these amine functional groups on the copolymer chain and the carboxyl group on N-carbobenzyloxy-phenylalanine (a protected amino acid). Although this method has been used to incorporate a particular amino acid onto the polymer chain, it maybe possible to extend this procedure to introduce virtually any amino acid or peptide group into the polymer chain. Finally a thermoplastic elastomer (TPE) was synthesized using the monomer (4-vinylphenyl)dimethylsilane. The first block of this TPE was a copolymer block of styrene with (4-vinylphenyl)dimethylsilane, followed by a polyisoprene block and finally another copolymer block of styrene and (4-vinylphenyl)dimethylsilane. This polymer was characterized using SEC, 1H and 13C NMR, FTIR, DSC, DMTA, TEM and tensile testing. It was seen to exhibit properties similar to those of a regular styrene-diene-styrene TPE. However, the silyl-hydride units introduced into this polymer chain can be easily converted to different functional groups using hydrosilation reactions. Introduction of such functional groups would be helpful in tailoring the properties of the TPE."--Abstract.
Author : Kwansoo Han
Publisher :
ISBN 13 :
Total Pages : 282 pages
Book Rating : 4.:/5 (365 download)
Download or read book Anionic Synthesis of Chain-end Functionalized Polymers written by Kwansoo Han and published by . This book was released on 1995 with total page 282 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Author : Christopher Michael Hurley
Publisher :
ISBN 13 :
Total Pages : 151 pages
Book Rating : 4.:/5 (975 download)
Download or read book Synthesis and Characterization of New Multifunctional Initiators for Anionic Polymerization and the Use of Poly(4-hydroxystyrene) as a Template for New Polymers written by Christopher Michael Hurley and published by . This book was released on 2016 with total page 151 pages. Available in PDF, EPUB and Kindle. Book excerpt: This dissertation explores the synthesis and use of multifunctional anionic polymerization initiators for the purpose of opening the gateway to the synthesis of polymer architectures of greater complexity. First the multifunctional oxyanion initiator generated by reacting poly(4-hydroxystyrene) with sodium hydride was used to synthesize a previously unknown polymer containing an aryl halide functional group. The homopolymer solution self-assembly behavior of poly(4-hydroxystyrene) and the newly synthesized poly (4-(4-bromophenyloxy)styrene) were both investigated. This is followed by the synthesis and characterization of multifunctional alkyne core molecules and random copolymers of polystyrene-co-poly(4-hydroxystyrene) which served as templates for the synthesis of new random copolymers of polystyrene-co-poly(4-(2- propynyloxy)styrene). The newly formed multifunctional alkyne core molecules and alkyne functionalized random copolymers served as polymer backbones in a "grafting to" strategy. Previously prepared azide terminated polymers were grafted to the multifunctional alkyne core molecules and polymer backbones by copper (I) catalyzed alkyne-azide cycloaddition reactions. Lastly, the synthesis of a new hydrocarbon soluble multifunctional initiator was undertaken. The resulting molecule was shown to be an efficient initiator of anionic polymerization in non-polar solvent in the absence of polar additives, necessary in all previous attempts to combat large scale aggregation of such multifunctional initiator. This new initiator will open the way to facile synthesis of well-defined star polymers, star-block copolymers, and more complex polymer architectures.
Author : Nikos Hadjichristidis
Publisher : Springer
ISBN 13 : 4431541861
Total Pages : 1075 pages
Book Rating : 4.4/5 (315 download)
Download or read book Anionic Polymerization written by Nikos Hadjichristidis and published by Springer. This book was released on 2015-09-01 with total page 1075 pages. Available in PDF, EPUB and Kindle. Book excerpt: This book presents these important facts: a) The mechanism of anionic polymerization, a more than 50-year challenge in polymer chemistry, has now become better understood; b) Precise synthesis of many polymers with novel architectures (triblock, multi-block, graft, exact graft, comb, cyclic, many armed stars with multi-components, dendrimer-like hyper-branched, and their structural mixed (co)polymers, etc.) have been advanced significantly; c) Based on such polymers, new morphological and self-organizing nano-objects and supra molecular assemblies have been created and widely studied and are considered nanodevices in the fields of nano science and technology; d) New high-tech and industrial applications for polymeric materials synthesized by anionic polymerization have been proposed. These remarkable developments have taken place in the last 15 years. Anionic polymerization continues to be the only truly living polymerization system (100 % termination free under appropriate conditions) and consequently the only one with unique capabilities in the synthesis of well-defined (i.e., precisely controlled molecular weight, nearly mono-disperse molecular weight distribution, structural and compositional homogeneity) complex macromolecular architectures. This book, with contributions from the world’s leading specialists, will be useful for all researchers, including students, working in universities, in research organizations, and in industry.
Author : Kevin Jiang
Publisher :
ISBN 13 :
Total Pages : 254 pages
Book Rating : 4.:/5 (957 download)
Download or read book Anionic Synthesis of Alkoxysilyl-functionalized Polymers written by Kevin Jiang and published by . This book was released on 2001 with total page 254 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Author : Jianxin Kuang
Publisher :
ISBN 13 :
Total Pages : 298 pages
Book Rating : 4.:/5 (353 download)
Download or read book Anionic Synthesis of Aldehyde, Amide and Amine Functionalized Polymers written by Jianxin Kuang and published by . This book was released on 1994 with total page 298 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Author : Gilda M. Lizarraga
Publisher :
ISBN 13 :
Total Pages : 212 pages
Book Rating : 4.:/5 (957 download)
Download or read book Anionic Synthesis and Functionalization of Dinaphthylalkyllithium End Functionalized Polystyrene written by Gilda M. Lizarraga and published by . This book was released on 1991 with total page 212 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Author : Surapich Loykulnant
Publisher :
ISBN 13 :
Total Pages : 250 pages
Book Rating : 4.:/5 (398 download)
Download or read book Precise Synthesis of Monosaccharide-functionalized Polymers by Means of Living Anionic Polymerization written by Surapich Loykulnant and published by . This book was released on 2001 with total page 250 pages. Available in PDF, EPUB and Kindle. Book excerpt:
