Radical Polymerizations II Special Cases
|
|
- Briana Gibbs
- 6 years ago
- Views:
Transcription
1 Radical Polymerizations II pecial Cases Devon A. hipp Department of Chemistry, & Center for Advanced Materials Processing Clarkson University Potsdam, NY Tel. (315) , Fax (315) Copyright 2016 Devon A. hipp 46
2 Living Polymerizations bjectives Continuous chain growth No termination Well-defined chains Chain structure Chain length Molecular weight distribution Block copolymer synthesis Requirements Initiation must be fast R i >> R p Termination must be eliminated r at least reduced to insignificance Problems with free radical polymerization Initiation is slow Radical-radical termination is fast 47
3 Reversible-Deactivation Radical Polymerizations (RDRP) ften called living radical polymerization Dormant polymer activation deactivation Active polymer radical + capping group Monomer (Propagation) Monomer repeat unit In Initiator (α) end Y Functional terminal (ω) end ("capping") group X n Y Molecular Weight DP = Δ[M] [In] 0 % Monomer Conversion Polydispersity <
4 Features of Living Polymerizations Linear increase in molecular weight Vs. monomer conversion Low polydispersity M w /M n < 1.5 (often ~ 1.1) Pre-defined molecular weight DP n = M n /FW M = Δ[M] / [Initiator] First-order monomer consumption ame as conventional radical polymerization 49
5 Terminology/Tests for Living Polymerization Controversy over terminology Controlled, living, pseudo-living, quasi-living, living/controlled, living/controlled, reversible-deactivation, IUPAC definition of living polymerization: Absence of irreversible transfer and termination Cannot be applied to any radical polymerization! ome tests for RDRP: Continued chain growth after addition monomer added Molecular weight increases linearly with conversion Active species (i.e. radicals) conc. remains constant Narrow molecular weight distributions (low M w /M n ) Block copolymers may be prepared (subset of first test) End groups are retained yields end-functionalized chains Moad and olomon The Chemistry of Radical Polymerization, 2 nd edition, 2006, page
6 Examples of RDRP Data Atom transfer radical polymerization (ATRP) tyrene. M n at 100% (theoretical) = 10,000 (DP = 100) T.E. Patten, J. Xia, T. Abernathy, K. Matyjaszewski, cience, 1996, 272, 866. K. Matyjaszewski, T.E. Patten, J. Xia, J. Am. Chem. oc., 1997, 119,
7 Calculated MWDs Moad and olomon The Chemistry of Radical Polymerization, 2 nd edition, 2006, page
8 Materials From RDRP D.A. hipp, Polym. Rev., 2011, 51,
9 RDRP: Types & Requirements Main types Nitroxide-Mediated Polymerization NMP Atom Transfer Radical Polymerization ATRP Reversible Addition- Fragmentation Chain Transfer Polymerization RAFT ther types Metal-mediated polymn Iniferter Group transfer polymn Requirements All chains begin at the same time Fast initiation Little or no termination Low radical concentration All chains grow at the same rate Fast exchange Iodo and methacrylate-based degenerate transfer 54
10 Nitroxide-Mediated Polymerization Nitroxides table free radicals P n -X Do not react with -centered radicals React fast with C-centered radicals k d ~ M -1 s -1 Do not initiate polymerization k a k d P n + X k p Monomer N Ph N TEMP 2,2,6,6 tetramethylpiperidim-noxyl nly good for styrene (co)polymers αh nitroxides tyrene, acrylates, acrylonitrile, 1,3- butadiene Rizzardo, olomon, et al. U Patent 4,581,429, Aust. J. Chem., 1990, 43, Chem. Aust., 1987, 54, 32. Ph n Ph Ph N k a k d Ph n Ph Ph Ph Propagation N TEMP 55
11 Georges/Xerox Approach to NMP BP n+1 Heat Ph Ph n Ph N TEMP Heat Ph n Ph N Ph n Ph N Propagation Molecular weight distributions of polystyrene produced by NMP using BP and TEMP. M n and M w /M n of samples I IV are as follows: (M n :M w /M n ) 1700:1.28, 3200:1.27, 6800:1.21, 7800:1.27. M.K. Georges et al., Macromolecules, 1993, 26,
12 Hawker Approach to NMP (Using TEMP) Alkoxyamine C.J. Hawker, J. Am. Chem. oc., 1994, 116,
13 Newer Nitroxides: α-hydrido-derivatives Wider range of monomers & functionalities Common nitroxides/ alkoxyamines cheme 3. Functional alkoxyamines P. Tordo, Y. Gnanau, et al., J. Am. Chem. oc., 2000, 122, C.J. Hawker, et al., J. Am. Chem. oc., 1999, 121, R.B. Grubbs, Polym. Rev., 2011, 51,
14 ffiffiffiffi The Persistent Radical Effect (PRE) Idea developed by H. Fischer, and furthered by T. Fukuda dr dt ¼ k di k c RY 2k t R 2 ; dy dt ¼ k di k c RY ¼ dr dt þ 2k tr 2 : Y ¼ð6k t K 2 eq I 2 0 Þ1=3 t 1=3 ; R ¼ K eqi 0 1=3t 1=3 6k t : 59 Chem. Rev. 2001, 101,
15 Consequences of the PRE Better control over polymer growth Faster deactivation Fewer radicals lower termination (R t ~ [R] 2 ) lower polymerization (R p ~ [R]) Better chain end functionalization dd polymerization kinetics Approx. t 1/3 dependence instead of t Can add some extra persistent radical (e.g. nitroxide) to improve PDI, slow rate, better end group control Chem. Rev. 2001, 101,
16 Atom Transfer Radical Polymerization Cu I Br + R R N N or N N N Metal catalyst (& ligand, L) Active propagating radical n Cu II Br 2 + ligand xidized metal catalyst P n -X + Mt q k a /L P n * + X-Mt q+1 /L k d P m * k p k t D + 2 X-Mt q+1 /L Monomer Dormant chain with halogen (X) n Br Dead chains H n n n m J.-. Wang, K. Matyjaszewski, J. Am. Chem. oc., 1995, 117, M. Kato, M. Kamigaito, M. awamoto, T. Higashimura, Macromolecules, 1995, 28, V. Percec, B. Barboiu, Macromolecules, 1995, 28,
17 Initiators for ATRP Best to copy end of growing polymer ATRP initiators ATRP polymers ther ATRP initiators used include: K. Matyjaszewski, J. Xia, Chem. Rev. 2001, 101,
18 Monomers for ATRP tyrenics Acrylates Methacrylates ther monomers, such nitriles, can be polymerized. Nucleophilic functionalities (e.g., amines, acids) can cause problems. K. Matyjaszewski, J. Xia, Chem. Rev. 2001, 101,
19 Catalysts for ATRP Ru, Ni, Fe & Cu Cu most used 64 K. Matyjaszewski, J. Xia, Chem. Rev. 2001, 101, Common ligands used with Cu ATRP catalysts based on other metals K. Matyjaszewski, N.V. Tsarevsky, Nat. Chem. 2009, 1,
20 Functional Polymers by ATRP End-group functionalization easy to perform with various alkyl halide reactions Click chemistries oup modifications Amine Epoxy Hydroxy Phosphines Macromers Vinyl K. Matyjaszewski, N.V. Tsarevsky, Nat. Chem. 2009, 1,
21 ome Mechanistic Details K Halogen exchange exch RBr + CuCl/L RCl + CBr/L Cl Br K. Matyjaszewski et al. Macromolecules 1998, 31,
22 How to Utilize Halogen Exchange Better control of homopolymerizations K. Matyjaszewski et al. Macromolecules 1998, 31,
23 Utilizing Halogen Exchange 2 Better block copolymers D.A. hipp, J.-L. Wang, K. Matyjaszewski Macromolecules 1998, 31,
24 Reverse ATRP Add regular initiator (e.g. AIBN), with oxidized metal (e.g. Cu II Br 2 ) & ligand Less trouble handling Cu II (c.f. Cu I ) Uses common initiator till provides good control, etc. Related to ICAR ATRP Initiators for continuous activator regeneration Allows for lower Cu concentrations J.-. Wang, K. Matyjaszewski Macromolecules, 1995, 28, K. Matyjaszewski et al. Proc. Natl. Acad. ci. U..A., 2006, 103,
25 Activator (Re)Generated by Electron Transfer (AGET & ARGET) ATRP Problem: use of Cu metal salts contaminates polymer Usually ends up being green Adds expense to polymerization vercome this by regenerating Cu(I) by using a reducing agent such as amines, glucose, ascorbic acid, etc., as well as Cu(0) wire Much lower [Cu] K. Matyjaszewski et al. Angew. Chem. Int. Ed. 2010, 49, Chem. Rev. 2007, 107,
26 ARA ATRP vs. ET LRP Controversy over ARGET-type approach ARA = supplemental regeneration of activators cheme 2 Key differences between the ARA ATRP mechanism and the ET-LRP mechanism. The ET-LRP mechanism assumes that Cu 0 is the major activator of alkyl halides (green dashed line) and that disproportionation (blue dashed line) is the dominant fate for Cu I complexes. ARA ATRP (red solid lines) assumes that Cu I is the major activator of alkyl halides and that Cu I species predominantly activate alkyl halides rather than disproportionate (reprinted with permission from ref. 72. Copyright 2014 the American Chemical ociety). 71 ARA-ATRP: Polym. Chem. 2014, 5, ET-LRP: Chem. Rev. 2009, 109,
27 eatrp Electrochemical ATRP Reduces Cu(II) A B B Fig. 4. (A) Conversion (solid circles) and applied potential (dashed line) with respect to time and (B) M n and M w /M n with respect to conversion. Toggling between active and dormant states is represented by changes of the E app values between 0.69V and 0.40 V versus Ag + /Ag, respectively. Reaction conditions are identical to those stated in Fig. 2. K. Matyjaszewski et al. cience 2011, 332,
28 ome Interesting Polymers from ATRP tars Macromolecules 2003, 36, Gradients & brushes MMA + HEMA-TM TM ATRP 1.ite Transformation to Macroinitiator Random Brush 2 Grafting From 1.ite Transformation to Macroinitiator 2 Grafting From Macromolecules 2002, 35, Continuous addition of HEMA-TM TM ATRP Gradient Brush 73
29 Degenerate Transfer Reversible chain transfer P m k tr P n + TG P n TG + P m k -tr k p monomer transfer group k p monomer Examples Iodine-mediated (TG = I atom) Methacrylic macromonomers Thiocarbonylthio (RAFT) polymerization 74
30 Iniferters 1 Initiator, transfer agent, terminator Disulfides High amounts of transfer Examples Diaryl disulfides Dithiuram disulfides (most successful) tsu et al. Makromol. Rapid Commun., 1983, 3, 127 & 133 X X Dithiocarbamyl end groups Thermally stable Photochemically labile N C C N 75
31 Iniferters 2 Initiation N C Δ or hν C N 2 N C Chain Transfer N C C N N C C N Termination / Reinitiation N C hν N C 76
32 RAFT Polymerization Reversible addition-fragmentation chain transfer Initiation / Chain Transfer I 2 Δ or hν P n monomer Z R CN C 2 CH 3 C N 2 CH 3 C 2 CH 3 Ph Ph dithioesters trithiocarbonates dithiocarbamates xanthates k add P n R P n R k β P n R k p Z k -add Z Z k p monomer monomer Chain equilibrium k add P n P m P n P m k β P n P m Z k -add Z Z k p k p monomer G. Moad, E. Rizzardo, et al., Macromolecules, 31, 5559 (1998) G. Moad, E. Rizzardo, et al., Patent W98/01478 (1998). Z. Zard et al. Patent W98/58974 (1998) monomer 77
33 Iodine & Methacrylic Macromonomers Iodine-mediated polymerizations Tatemoto (Eur. Patent A1, 1992) Matyjaszewski (Macromolecules, 1995, 28, pp and 8051) P m k tr P n + I P n I + P m k -tr k p monomer Polymerization of vinyl acetate Iovu & Matyjaszewski (Macromolecules, 2003, 35, 9346) k p monomer 78
34 Macromonomer Method Methacrylate-based macromonomers Moad et al. (Macromolecules, 1996, 29, 7717) k P Pm add n P n P m k β P n P m k p C 2 CH 3 k β C 2 CH 3 k add C 2 CH 3 k p monomer monomer 79
35 Macromonomer Mechanism Moad et al. Macromolecules, 1996, 29,
36 rganoheteroatom-mediated Polymerization rganotellurium A. Goto et al. JAC, 2003, 125, 8720 rganostibine. Yamago et al. JAC, 2004, 126, rganobismuthin. Yamago et al. Angew. Chem. Int. Ed., 2007, 46, 1304 Two concurrent mechanisms:. Yamago Chem. Rev., 2009, 109,
37 Cobalt-Mediated Polymerization rganometallic mediated polymerization (MRP) Various metals can be used (Ti, V, Fe, s, Mo, Cr) but most successful is Co Co-mediated polymerization mechanism depends on conditions Degenerate transfer (DT) if high radical conc. Reversible-deactivation (RD) if low radical conc. Largely works for vinyl acetate & acrylates Ti okay for MMA and derivative 82
SS Vorlesung Polymermaterialien Polymerisationsmethoden
Professur Polymerchemie SS 2017 Vorlesung Prof. Michael Sommer 1 www.tu-chemnitz.de Content Free radical polymerization (PS, PMMA) Controlled radical polymerization Ionic polymerization (cationic, anionic)
More informationIntroduction to Macromolecular Chemistry
Introduction to Macromolecular Chemistry aka polymer chemistry Mondays, 8.15-9.45 am except for the following dates: 01.+29.05, 05.+12.06., 03.07. Dr. Christian Merten, Ruhr-Uni Bochum, 2017 www.ruhr-uni-bochum.de/chirality
More informationInvestigating Nitroxide-Mediated Radical Polymerization of Styrene over a Range of Reaction Conditions
Investigating Nitroxide-Mediated Radical Polymerization of Styrene over a Range of Reaction Conditions A. Nabifar N. T. McManus A. Penlidis Institute for Polymer Research (IPR) Department of Chemical Engineering
More informationMacromolecular Chemistry
Macromolecular Chemistry N N N Cu + BR - N Lecture 7 Decomposition of Thermal Initiator k d I 2 R Efficiency factor ( f ): CN N N CN di-tert-butylperoxide AIBN di-tert-butylperoxalate f = 0.65 f = 0.75
More informationCh1. Introduction Types of Polymers and Polymerization. : formed from polyfunctional monomers by
Ch1. Introduction 1-1. Types of Polymers and Polymerization a. Polymer Composition and Structure - Condensation Polymer : formed from polyfunctional monomers by condensation reactions with the elimination
More informationState-of-the-Art and Progress in Method of Moments for the Model-Based Reversible- Deactivation Radical Polymerization
Review State-of-the-Art and Progress in Method of Moments for the Model-Based Reversible- Deactivation Radical Polymerization Yin-Ning Zhou, Zheng-Hong Luo* Reversible-deactivation radical polymerization
More informationControlled Polymerizations
Wednesday Meeting Controlled Polymerizations 10/15/2014 Ki-Young Yoon Organometallics : A Friend of Total Synthesis Total Synthesis Organometallics e.g. Barry Trost Organometallics : A Friend of Polymer
More informationLIVING/CONTROLLED RADICAL POLYMERIZATION IN A CONTINUOUS TUBULAR REACTOR
LIVING/CONTROLLED RADICAL POLYMERIZATION IN A CONTINUOUS TUBULAR REACTOR by THOMAS EDWARD ENRIGHT A thesis submitted to the Department of Chemical Engineering In conformity with the requirements for the
More informationARGET ATRP of copolymerization of styrene and acrylonitrile with environmentally friendly catalyst and ligand
e-polymers 2011, no. 054 http://www.e-polymers.org ISSN 1618-7229 ARGET ATRP of copolymerization of styrene and acrylonitrile with environmentally friendly catalyst and ligand Guoxiang Wang, 1* Mang Lu
More informationCopper-Mediated Atom Transfer Radical Polymerisation (ATRP) of Acrylates in Protic Solution.
Copper-Mediated Atom Transfer Radical Polymerisation (ATRP) of Acrylates in Protic Solution. Laura. Pilon *, Steven P. Armes *, Paul Findlay, Steven Rannard. * School of Chemistry, Physics and Environmental
More informationA Little Bit on Polymers and More on Radical Polymerizations
Leo Hendrick Baekeland The Bakelizer A Little Bit on Polymers and More on Radical Polymerizations Justin Barry Group Meeting 10/7/2015 Overview of Presentation Global demand Polymerization Basic nomenclature
More informationATOM TRANSFER RADICAL POLYMERIZATION WITH LOW CATALYST CONCENTRATION IN CONTINUOUS PROCESSES
ATOM TRANSFER RADICAL POLYMERIZATION WITH LOW CATALYST CONCENTRATION IN CONTINUOUS PROCESSES by NICKY C. F. CHAN A thesis submitted to the Department of Chemical Engineering In conformity with the requirements
More informationSwitchable Catalysis
Switchable Catalysis hν 1 hν 2 Tiffany Chen MacMillan Lab June 5, 2018 Switchable Catalysis: Inspiration from ature the synthetic machinery of natural systems makes complex polymers with fine temporal
More informationCONTROLLED RADICAL POLYMERIZATION IN THE DISPERSED PHASE
CONTROLLED RADICAL POLYMERIZATION IN THE DISPERSED PHASE by MARY E. THOMSON A thesis submitted to the Department of Chemical Engineering in conformity with the requirements for the degree of Doctor of
More informationSynthesis and Controlled Radical Polymerization of Multifunctional Monomers
Synthesis and Controlled Radical Polymerization of Multifunctional Monomers Meizhen Yin Technischen Universität Dresden June 2004 Synthesis and Controlled Radical Polymerization of Multifunctional Monomers
More informationMechanism of Controlled/ Living Radical Polymerization of Styrene in the Presence of Nitroxyl Radicals. Kinetics and Simulations
Macromolecules 1996, 29, 7661-7670 7661 Mechanism of Controlled/ Living Radical Polymerization of Styrene in the Presence of Nitroxyl Radicals. Kinetics and Simulations Dorota Greszta and Krzysztof Matyjaszewski*
More informationGuo-Xiang Wang Mang Lu Jing Li Li-Chao Liu Bei-Ping Luo Hu Wu Ming Zhong
Iran Polym J (2013) 22:109 116 DOI 10.1007/s13726-012-0109-z ORIGINAL PAPER Copolymerization of styrene and methyl methacrylate mediated by iron wire/n,n,n 0,N 0 -tetramethyl-1,2-ethanediamine as catalyst
More informationVolume 31, Number 23 November 17, Copper Triflate as a Catalyst in Atom Transfer Radical Polymerization of Styrene and Methyl Acrylate
Volume 31, Number 23 November 17, 1998 Copyright 1998 by the American Chemical Society Copper Triflate as a Catalyst in Atom Transfer Radical Polymerization of Styrene and Methyl Acrylate Brian E. Woodworth,
More informationMODELING AND PARAMETER ESTIMATION OF NITROXIDE MEDIATED LIVING FREE RADICAL POLYMERIZATION (NMRP) OF STYRENE
European Symposium on Computer Aided Process Engineering 15 L. Puigjaner and A. Espuña (Editors) 25 Elsevier Science B.V. All rights reserved. MODELING AND PARAMETER ESTIMATION OF NITROXIDE MEDIATED LIVING
More informationAtom transfer radical polymerization (ATRP) of styrene and methyl methacrylate with a,a-dichlorotoluene as initiator; a kinetic study
980 Macromol. Chem. Phys. 201, 980 984 (2000) Full Paper: The atom transfer radical polymerization (ATRP) of styrene and methyl methacrylate with a,adichlorotoluene (DCT) as initiator results in the respective
More informationLiving p-quinodimethane Polymerization for the Synthesis of Well-Defined PPV Materials: Progress and Challenges
Living p-quinodimethane Polymerization for the Synthesis of Well-Defined PPV Materials: Progress and Challenges Thomas Junkers Hasselt University Wetenschapspark 1 BE 3590 Diepenbeek www.polymatter.net
More informationControlled polymerization of methylmethacrylate and ethylacrylate using tris
Controlled polymerization of methylmethacrylate and ethylacrylate using tris(4,4'-dimethyl-2,2'-bipyridine) copper(ii) hexafluorophosphate complexes and aluminium isopropoxide Ulrich S. Schubert ( ), Georg
More informationProgresses in Reactor Engineering of Controlled Radical Polymerization: A Comprehensive Review
Progresses in Reactor Engineering of Controlled Radical Polymerization: A Comprehensive Review Journal: Manuscript ID RE-REV-0-0-0000.R Article Type: Review Article Date Submitted by the Author: 0-Nov-0
More informationSupported cobalt mediated radical polymerization (SCMRP) of vinyl acetate and recycling of the cobalt complex 1
Supported cobalt mediated radical polymerization (SCMRP) of vinyl acetate and recycling of the cobalt complex 1 Valérie Sciannamea, Antoine Debuigne, Yasmine Piette, Robert Jérôme and Christophe Detrembleur
More informationCationic Polymerization
10.569 Synthesis of Polymers Prof. Paula Hammond Lecture 26: Cationic ing pening Polymerization, ther ing pening Polymerization Cationic Polymerization Kk i k p [][ I ZY ][ M ] 2 = p k t Energetics of
More informationRAFT Fundamentals A History and Recent Developments CSIRO Manufacturing Flagship
RAFT Fundamentals A History and Recent Developments CIRO Manufacturing Flagship Graeme Moad MACRO 2016 Istanbul 17 July 2016 CIRO MANUFACTURING Outline RAFT Polymerization Description and History RAFT
More informationComprehensive Modeling Study of Nitroxide-Mediated Controlled/Living Radical Copolymerization of Methyl Methacrylate with a Small Amount of Styrene
4470 Macromolecules 2009, 42, 4470 4478 DOI: 10.1021/ma900515v Comprehensive Modeling Study of Nitroxide-Mediated Controlled/Living Radical Copolymerization of Methyl Methacrylate with a Small Amount of
More informationPolymerisation of Sodium 4-Styrenesulfonate via Atom Transfer Radical Polymerisation
Polymerisation of Sodium 4-Styrenesulfonate via Atom Transfer Radical Polymerisation Peter D. Iddon, Kay L. Robinson and Steven P. Armes ACS Philadelphia Meeting August 2004 Email: P.Iddon@shef.ac.uk Introduction
More informationAubrey D. Jenkins 1, Richard G. Jones 2,, and Graeme Moad 3,
Pure Appl. Chem., Vol. 82, No. 2, pp. 483 491, 2010. doi:10.1351/pac-rep-08-04-03 2009 IUPAC, Publication date (Web): 18 November 2009 Terminology for reversible-deactivation radical polymerization previously
More informationIPR 2009 UNIVERSIDAD NACIONAL. Gabriel Jaramillo-Soto. Prof. Eduardo Vivaldo Lima
UNIVERSIDAD NACIONAL AUTÓNOMA DE MÉXICOM PROGRAMA DE DOCTORADO EN INGENIERÍA FACULTAD DE QUÍMICA Reversible Addition-Fragmentation chain Transfer (RAFT) polymerization in supercritical Carbon Dioxide (scco
More informationSynthesis of Random Copolymers Poly (methylmethacrylate-co-azo monomer) by ATRP-AGET
Macromol. Symp. 2009, 283 284, 51 55 DI: 10.1002/masy.200950908 51 Synthesis of Random Copolymers Poly (methylmethacrylate-co-azo monomer) by ATRP-AGET M.A. ájera, L.E. Elizalde,* Y. Vázquez, G. de los
More informationRadical Initiation 2017/2/ ) Thermal Decomposition of Initiators
adical Initiation Production of radicals (from initiator) to initiate chain polymerization. A variety of initiator systems can be used to bring about the radical polymerization. 1) Thermal Decomposition
More informationEffect of Molecular Structure of Side Chain Polymers on "Click" Synthesis of Thermosensitive Molecular Brushes
University of Tennessee, Knoxville Trace: Tennessee Research and Creative Exchange University of Tennessee Honors Thesis Projects University of Tennessee Honors Program 5-2017 Effect of Molecular Structure
More informationTowards Biocompatible Shell Cross-Linked Micelles
Towards Biocompatible Shell Cross-Linked Micelles Colin D Turner, Steven P Armes, Andrew L Lewis School of Chemistry, Physics and Environmental Science, University of Sussex, Falmer, Brighton, BN1 9QJ,
More informationOptimization of Atom Transfer Radical Polymerization Using Cu(I)/ Tris(2-(dimethylamino)ethyl)amine as a Catalyst
Macromolecules 2000, 33, 8629-8639 8629 Optimization of Atom Transfer Radical Polymerization Using Cu(I)/ Tris(2-(dimethylamino)ethyl)amine as a Catalyst Jerome Queffelec, Scott G. Gaynor, and Krzysztof
More informationPolymer 49 (2008) Contents lists available at ScienceDirect. Polymer. journal homepage:
Polymer 9 (8) 177 18 Contents lists available at ScienceDirect Polymer journal homepage: www.elsevier.com/locate/polymer Feature Article Reversible chain transfer catalyzed polymerization (RTCP): A new
More informationAtom Transfer Radical Polymerization of Hexadecyl Acrylate Using CuSCN as the Catalyst
Macromolecular Research, Vol. 12, No. 1, pp 32-37 (2004) Atom Transfer Radical Polymerization of Hexadecyl Acrylate Using CuSCN as the Catalyst Wenjian Xu, Xiulin Zhu*, Zhenping Cheng, Jianying Chen, and
More informationAnionic Polymerization - Initiation and Propagation
Anionic Polymerization Initiation and Propagation As in free radical polymerization, there are initiation and propagation steps. NH 2 NaNH 2 Na + + NH 2 + H 2 N CH: Propagation proceeds in the usual manner,
More informationVisible Light-Induced Atom Transfer Radical Polymerization for Macromolecular Syntheses
Chapter 8 Visible Light-Induced Atom Transfer Radical Polymerization for Macromolecular Syntheses Downloaded by YALE UNIV on May 14, 2015 http://pubs.acs.org Yusuf Yagci, 1,2,* Mehmet Atilla Tasdelen,
More informationSynthesis of methacrylate macromonomers using silica gel supported atom transfer radical polymerization
Macromol. Chem. Phys. 2000, 201, 1387 1394 1387 Full Paper: A silica gel supported CuBr-hexamethyltriethylenetetramine (HMTETA) (SG-CuBr/HMTETA) catalyst system was developed for the synthesis of poly-
More informationKinetic Studies on Bulk Atom Transfer Radical Polymerization of Styrene
American Journal of Polymer Science and Technology 2017; 3(6): 103-107 http://www.sciencepublishinggroup.com/j/ajpst doi: 10.11648/j.ajpst.20170306.12 ISSN: 2575-5978 (Print); ISSN: 2575-5986 (Online)
More informationSupplemental Information
Electronic Supplementary Material (ESI) for RSC Advances. This journal is The Royal Society of Chemistry 2015 Supplemental Information Influence of Less Active Initiator on the Living Performance of Atom
More informationTHE CHEMISTRY OF RADICAL POLYMERIZATION
THE CHEMISTRY OF RADICAL POLYMERIZATION THE CHEMISTRY OF RADICAL POLYMERIZATION GRAEME MOAD CSIRO Molecular and Health Technologies Bayview Ave, Clayton, Victoria 3168, AUSTRALIA and DAVID H. SOLOMON
More informationSynthesis and Characterization of Silsesquioxane-Based Polymer Hybrids with Controlled Structure
Vol. Materials 5, No. Research, 3, 2002Vol. 5, No. Synthesis 3, 247-252, and 2002. Characterization of Silsesquioxane-Based Polymer Hybrids with Controlled Structure 2002 247 Synthesis and Characterization
More informationProteins as Initiators of Controlled Radical Polymerization: Graftingfrom via ATRP and RAFT Brent S. Sumerlin*
pubs.acs.org/macroletters Proteins as Initiators of Controlled Radical Polymerization: Graftingfrom via ATRP and RAFT Brent S. Sumerlin* Department of Chemistry and Center for Drug Discovery, Design, and
More informationSynthesis of Bottlebrush Polymers Using the Grafting-Through and Transfer-To Methods. Scott Charles Radzinski
Synthesis of Bottlebrush Polymers Using the Grafting-Through and Transfer-To Methods Scott Charles Radzinski Dissertation submitted to the faculty of the Virginia Polytechnic Institute and State University
More informationMATLAB Programming of Polymerization Processes using Monte Carlo Techniques
35 MATLAB Programming of Polymerization Processes using Monte Carlo Techniques Mamdouh A. Al-Harthi Chemical Engineering Department, King Fahd University of Petroleum & Minerals, Dhahran 31261, Saudi Arabia
More informationSimulating Controlled Radical Polymerizations with mcpolymer A Monte Carlo Approach
Polymers 2012, 4, 1416-1442; doi:10.3390/polym4031416 Article OPEN ACCESS polymers ISSN 2073-4360 www.mdpi.com/journal/polymers Simulating Controlled Radical Polymerizations with mcpolymer A Monte Carlo
More informationMacromolecular Design via Reversible Addition Fragmentation Chain Transfer (RAFT)/Xanthates (MADIX) Polymerization
HIGHLIGHT Macromolecular Design via Reversible Addition Fragmentation Chain Transfer (RAFT)/Xanthates (MADIX) Polymerization SÉBASTIEN PERRIER, PITTAYA TAKOLPUCKDEE Department of Colour and Polymer Chemistry,
More informationComparison between Polymerization Techniques for synthesis of Energetic Thermoplastic Elastomers. Khalifa Al-Kaabi and Albert Van Reenen
Comparison between Polymerization Techniques for synthesis of Energetic Thermoplastic Elastomers Khalifa Al-Kaabi and Albert Van Reenen Department for Chemistry and Polymer Science, University of Stellenbosch,
More informationAtom Transfer Radical Polymerization of 2-Hydroxyethyl Methacrylate
5772 Macromolecules 1999, 32, 5772-5776 Atom Transfer Radical Polymerization of 2-Hydroxyethyl Methacrylate Kathryn L. Beers, Sohyun Boo, Scott G. Gaynor, and Krzysztof Matyjaszewski* Center for Macromolecular
More informationRAFT Polymerization Kinetics of α-methylbenzyl Methacrylate by Dilatometry
Journal of Materials cience Research; Vol. 1, No. 3; 2012 IN 1927-0585 E-IN 1927-0593 Published by Canadian Center of cience and Education RAFT Polymerization Kinetics of α-methylbenzyl Methacrylate by
More informationCu(II)-Mediated ATRP of MMA by Using a Novel Tetradentate Amine Ligand with Oligo(ethylene glycol) Pendant Groups
Communication Cu(II)-Mediated ATRP of MMA by Using a Novel Tetradentate Amine Ligand with Oligo(ethylene glycol) Pendant Groups Caglar Remzi Becer, Richard Hoogenboom, David Fournier, Ulrich S. Schubert*
More informationRadical Polymerization and Click Chemistry. Surfaces using Gamma Irradiation. Supporting Information*
Synthesis of Block Copolymers via Atom Transfer Radical Polymerization and Click Chemistry grafted from Pre-functionalized Polypropylene Surfaces using Gamma Irradiation Supporting Information* Ollie Foster,
More informationMolecular Weight and Chain Transfer
1 Molecular Weight and Chain Transfer Kinetic Chain Length ( ): 動力學鏈長 Average number of monomer polymerized per radical, which initiates a polymer chain. = R p /R i = R p /R t = k p [M][M.]/2k t [M.] 2
More informationIUPAC INTERNATIONAL UNION OF PURE AND APPLIED CHEMISTRY POLYMER DIVISION SUB-COMMITTEE ON POLYMER TERMINOLOGY*
Page of 0 0 0 0 0 0 Pure Appl. Chem., Vol. INTERNATIONAL UNION OF PURE AND APPLIED CHEMISTRY POLYMER DIVISION SUB-COMMITTEE ON POLYMER TERMINOLOGY* TERMINOLOGY FOR RADICAL POLYMERIZATIONS WITH MINIMAL
More informationSynthesis of Complex Macromolecules Using Iterative Copper(0)-Mediated Radical Polymerization
JOURNAL OF POLYMER SCIENCE WWW.POLYMERCHEMISTRY.ORG HIGHLIGHT Synthesis of Complex Macromolecules Using Iterative Copper(0)-Mediated Radical Polymerization Cyrille Boyer, 1 Per B. Zetterlund, 1 Michael
More informationOptimization of the Nitroxide-Mediated Radical Polymerization Conditions for Styrene and tert-butyl Acrylate in an Automated Parallel Synthesizer
Optimization of the Nitroxide-Mediated Radical Polymerization Conditions for Styrene and tert-butyl Acrylate in an Automated Parallel Synthesizer C. REMZI BECER, RENZO M. PAULUS, RICHARD HOOGENBOOM, ULRICH
More informationReaction chemistry of complexes Three general forms: 1. Reactions involving the gain and loss of ligands a. Ligand Dissoc. and Assoc. (Bala) b.
eaction chemistry of complexes Three general forms: 1. eactions involving the gain and loss of ligands a. Ligand Dissoc. and Assoc. (Bala) b. Oxidative Addition c. eductive Elimination d. Nucleophillic
More informationOn Chain-Length Dependence in Living Radical Polymerizations: A Trip to Monte Carlo
On Chain-Length Dependence in Living Radical Polymerizations: A Trip to Monte Carlo Originally published as: Chain-Length Dependence in Controlled/Living Radical Polymerizations: Physical Manifestation
More informationChapter 5. Ionic Polymerization. Anionic.
Chapter 5. Ionic Polymerization. Anionic. Anionic Polymerization Dr. Houston S. Brown Lecturer of Chemistry UH-Downtown brownhs@uhd.edu What you should know: What is anionic polymerization? What is MWD,
More informationAdvanced Materials by Atom Transfer Radical Polymerization
REVIEW Hall of Fame Article Advanced Materials by Atom Transfer Radical Polymerization Krzysztof Matyjaszewski Atom transfer radical polymerization (ATRP) has been successfully employed for the preparation
More informationRAFT Polymerization of a Novel Activated Ester Monomer and Conversion to a Terpyridine-Containing Homopolymer
RAFT Polymerization of a Novel Activated Ester Monomer and Conversion to a Terpyridine-Containing Homopolymer KHALED A. AAMER, GREGORY N. TEW Department of Polymer Science and Engineering, University of
More informationModel-based optimization of polystyrene properties by Nitroxide Mediated Polymerization (NMP) in homogeneous and dispersed media
1 Model-based optimization of polystyrene properties by Nitroxide Mediated Polymerization (NMP) in homogeneous and dispersed media Lien Bentein NMP: principle and objective Nitroxide mediated polymerization
More informationPolymer 54 (2013) 981e994. Contents lists available at SciVerse ScienceDirect. Polymer. journal homepage:
Polymer 54 (2013) 981e994 Contents lists available at SciVerse ScienceDirect Polymer journal homepage: www.elsevier.com/locate/polymer Feature article Recent progress in the use of photoirradiation in
More informationTitle From NMP to RAFT and Thiol-Ene Chemistry by In Situ Functionalization of Nitroxide Chain Ends
biblio.ugent.be The UGent Institutional Repository is the electronic archiving and dissemination platform for all UGent research publications. Ghent University has implemented a mandate stipulating that
More informationUniversity of Groningen. Rheokinetics Cioffi, Mario
University of Groningen Rheokinetics Cioffi, Mario IMPORTANT NOTE: You are advised to consult the publisher's version (publisher's PDF) if you wish to cite from it. Please check the document version below.
More informationSynthesis of Controlled Polymer Nanospheres by a Reversible Addition- Fragmentation Chain Transfer (RAFT) Miniemulsion Polymerization
Synthesis of Controlled Polymer Nanospheres by a Reversible Addition- Fragmentation Chain Transfer (RAFT) iniemulsion Polymerization Huije Lee, Sang Eun Shim, Byung H. Lee, Soonja Choe* Department of Chemical
More informationPII: S (97)
PII: S0032-3861(97)10176-8 Polymer Vol. 39 No. 21, pp. 5163 5170, 1998 0032-3861/98/$ see front matter 1998 Elsevier Science Ltd. All rights reserved. Development of novel attachable initiators for atom
More informationProbing mechanistic features of conventional, catalytic and living free radical polymerizations using soft ionization mass spectrometric techniques
Polymer 45 (2004) 7791 7805 Feature Article Probing mechanistic features of conventional, catalytic and living free radical polymerizations using soft ionization mass spectrometric techniques Christopher
More informationRe(V)-Mediated Living Radical Polymerization of Styrene: 1 ReO 2 I(PPh 3 ) 2 /R-I Initiating Systems
2420 Macromolecules 1999, 32, 2420-2424 Re(V)-Mediated Living Radical Polymerization of Styrene: 1 ReO 2 I(PPh 3 ) 2 /R-I Initiating Systems Yuzo Kotani, Masami Kamigaito, and Mitsuo Sawamoto* Department
More informationScheme 1. [2, 5,7] 1,10-phenantrolines, [6] aryl/alkyl-2-pyridylmethanimines
Macromol. Rapid Commun. 2000, 21, 1337 1341 1337 Communication: The effect of the nature of initiator and solvent in atom transfer radical polymerization of methyl methacrylate (MMA) using N-pentyl-2-pyridylmethanimine
More informationAtom Transfer Radical Polymerization: Billion Times More Active Catalysts and New Initiation Systems
REVIEW 25 Years of ATRP Atom Transfer Radical Polymerization: Billion Times More Active Catalysts and New Initiation Systems Thomas G. Ribelli, Francesca Lorandi, Marco Fantin, and Krzysztof Matyjaszewski*
More informationOrganic & Biomolecular Chemistry
Organic & Biomolecular Chemistry REVIEW Cite this: Org. Biomol. Chem., 2014, 12, 8580 Reversible deactivation radical polymerization mediated by cobalt complexes: recent progress and perspectives Chi-How
More informationReversible Addition-Fragmentation Chain Transfer-Hetero Diels- Alder (RAFT-HDA) Chemistry as an Efficient Conjugation
Reversible Addition-Fragmentation Chain Transfer-Hetero Diels- Alder (RAFT-HDA) Chemistry as an Efficient Conjugation Technique for Macromolecular Surface Engineering Zur Erlangung des akademischen Grades
More informationEnd-Functional Poly(tert-butyl acrylate) Star Polymers by Controlled Radical Polymerization
2340 Macromolecules 2000, 33, 2340-2345 End-Functional Poly(tert-butyl acrylate) Star Polymers by Controlled Radical Polymerization Xuan Zhang, Jianhui Xia, and Krzysztof Matyjaszewski* Center for Macromolecular
More informationLecture 27 More Polymers
Lecture 27 More Polymers Step Chain April 26, 2016 Midterm Exam III Where: WEL 1.316!! When: Wed., May 4 th, 7:00 9:00 PM What: Covers lectures through 4/28 Review Session: Mon & Tues. 5-6 PM Monday PAI
More information-Cyanobenzyl Dithioester Reversible Addition Fragmentation Chain-Transfer Agents for Controlled Radical Polymerizations
-Cyanobenzyl Dithioester Reversible Addition Fragmentation Chain-Transfer Agents for Controlled Radical Polymerizations CHUNZHAO LI, BRIAN C. BENICEWICZ NYS Center for Polymer Synthesis, Department of
More informationIntroduction to Polymerization Processes
Introduction to Polymerization Processes Reference: Aspen Polymers: Unit Operations and Reaction Models, Aspen Technology, Inc., 2013. 1- Polymer Definition A polymer is a macromolecule made up of many
More information1.1 Basic Polymer Chemistry. 1.2 Polymer Nomenclature. 1.3 Polymer Synthesis. 1.4 Chain Growth Polymerization. Polymer =
1.1 Basic Polymer hemistry Polymers are the largest class of soft materials: over 100 billion pounds of polymers made in US each year lassification systems 1.2 Polymer Nomenclature Polymer = Monomer =
More informationJung Min Lee, Ok Hyung Kim, Sang Eun Shim, Byung H. Lee, and Soonja Choe* Department of Chemical Engineering, Inha University, Inchon , Korea
Macromolecular Research, Vol. 13, No. 3, pp 36-4 (005) Reversible Addition-Fragmentation Chain Transfer (RAFT) Bulk Polymerization of Styrene : Effect of R-Group Structures of Carboxyl Acid Group Functionalized
More informationSeminar Series. Vinyl Acetate Radical Polymerization Kinetics Studies
Vinyl Acetate Radical Polymerization Kinetics Studies Otlaatla Monyatsi Pulsed-laser polymerization (PLP) combined with analysis of the resulting polymer molecular mass distribution (MMD) is used to measure
More informationChemical Engineering Seminar Series
Effect of Reaction Conditions on Copolymer Properties Loretta Idowu Keywords: copolymer composition distribution; radical polymerization kinetics; semi-batch starved feed; hydroxyl-functionality Non-functional
More informationBehavior of 3-Vinylpyridine in Nitroxide-Mediated Radical Polymerization: The Influence of Nitroxide Concentration, Solvent, and Temperature
Behavior of 3-Vinylpyridine in Nitroxide-Mediated Radical Polymerization: The Influence of Nitroxide Concentration, Solvent, and Temperature XING ZHE DING, 1 ARNAUD FISCHER, 1 ALAIN BREMBILLA, 2 PIERRE
More informationS. Pascual, B. Coutin, M. Tardi, A. Polton, and J.-P. Vairon*
1432 Macromolecules 1999, 32, 1432-1437 Homogeneous Atom Transfer Radical Polymerization of Styrene Initiated by 1-Chloro-1-phenylethane/Copper(I) Chloride/Bipyridine in the Presence of Dimethylformamide
More informationSILOXYL AND HYDROXYL FUNCTIONALIZED POLYMERS BY ATOM TRANSFER RADICAL POLYMERIZATION NOMFUSI AUGUSTA MPUTUMANA
SILXYL AND YDRXYL FUNTINALIZED PLYMERS BY ATM TRANSFER RADIAL PLYMERIZATIN BY NMFUSI AUGUSTA MPUTUMANA submitted in accordance with the requirements for the degree of MASTER F SIENE in the subject EMISTRY
More informationSpin Capturing with Nitrones: Radical Coupling Reactions with Concurrent Introduction of Midchain Functionality
Supplementary Information: Spin Capturing with Nitrones: Radical Coupling Reactions with Concurrent Introduction of Midchain Functionality Edgar H. H. Wong, a,b Cyrille Boyer, b Martina H. Stenzel, b Christopher
More informationOrganometallic Catalysis
Organometallic Catalysis The catalysts we will study are termed homogeneous catalysts as they are dissolved in th e same solvent as the substrate. In contrast, heterogeneous catalysts, such as palladium
More informationRepeated insertion. Multiple insertion leads to dimerization, oligomerization or polymerization. κ 1: mainly dimerization κ
Repeated insertion ultiple insertion leads to dimerization, oligomerization or polymerization. k prop Et Key factor: k CT / k prop = κ κ 1: mainly dimerization κ 0.1-1.0: oligomerization (always mixtures)
More informationSYNTHESIS OF MODEL RANDOM POLYAMPHOLYTES LARISSA NITA D SOUZA. Bachelor of Science in Chemistry University of Bombay Bombay, India 1992
SYNTHESIS OF MODEL RANDOM POLYAMPHOLYTES By LARISSA NITA D SOUZA Bachelor of Science in Chemistry University of Bombay Bombay, India 1992 Master of Science in Chemistry Oklahoma State University Stillwater,
More informationSynthesis of C 60 End-Capped Polymers from Azide Functional Polystyrene via Atom Transfer Radical Polymerization
Synthesis of C 60 End-Capped Polymers from Azide Functional Polystyrene via Atom Transfer Radical Polymerization LANG LI, CHANGCHUN WANG, ZHAOHUI LONG, SHOUKUAN FU Department of Macromolecular Science
More informationMacromolecular Chemistry
Macromolecular Chemistry Lecture 5 Step Growth Chain Growth Paul Flory Clears Things Up Polymer Structure is distinct from polymerization process Addition Polymerization H H Condensation Polymerization
More informationKinetics and Mechanism of Cu-Catalyzed Atom Transfer Radical Polymerization
Kinetics and Mechanism of Cu-Catalyzed Atom Transfer Radical Polymerization Dissertation zur Erlangung des mathematisch-naturwissenschaftlichen Doktorgrades Doctor rerum naturalium der Georg-August-Universität
More informationEXPERIMENTAL AND MODELING STUDIES OF DIFFUSION- CONTROLLED REACTIONS IN ATOM TRANSFER RADICAL POLYMERIZATION AT HIGH CONVERSION
EXPERIMENTAL AND MODELING STUDIES OF DIFFUSION- CONTROLLED REACTIONS IN ATOM TRANSFER RADICAL POLYMERIZATION AT HIGH CONVERSION EXPERIMENTAL AND MODELING STUDIES OF DIFFUSION- CONTROLLED REACTIONS IN ATOM
More informationNITROXIDE MEDIATED POLYMERIZATION: MICROEMULSION OF N-BUTYL ACRYLATE AND THE SYNTHESIS OF BLOCK COPOLYMERS
NITROXIDE MEDIATED POLYMERIZATION: MICROEMULSION OF N-BUTYL ACRYLATE AND THE SYNTHESIS OF BLOCK COPOLYMERS by Wing Sze Jennifer Li A thesis submitted to the Department of Chemical Engineering In conformity
More informationAB DIBLOCK COPOLYMER NANOPARTICLES VIA RAFT-MEDIATED POLYMERIZATION AS A PSEUDOSTATIONARY PHASE FOR ELECTROKINETIC CHROMATOGRAPHY
University of Montana ScholarWorks at University of Montana Graduate Student Theses, Dissertations, & Professional Papers Graduate School 2012 AB DIBLOCK COPOLYMER NANOPARTICLES VIA RAFT-MEDIATED POLYMERIZATION
More informationBlock copolymers with polar and non-polar blocks : combination of living anionic polymerization and RAFTmediated
Block copolymers with polar and non-polar blocks : combination of living anionic polymerization and RAFTmediated polymerization Donkers, E.H.D. DOI: 10.6100/IR609506 Published: 01/01/2006 Document Version
More informationDepartment of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue, Pittsburgh, Pennsylvania 15213
Block Copolymers by Transformation of Living Carbocationic into Living Radical Polymerization. II. ABA-Type Block Copolymers Comprising Rubbery Polyisobutene Middle Segment SIMION COCA, KRZYSZTOF MATYJASZEWSKI
More informationNMR studies of styreneln-butyl acrylate copolymers prepared by atom transfer radical polymerization
Indian Journal o Chemistry Vol. 43A, November 2004, pp. 2281-2286 NMR studies o styreneln-butyl acrylate copolymers prepared by atom transer radical polymerization A S Brar* & Puneeta Department o Chemistry,
More informationLiving Radical Polymerization via Organic Superbase Catalysis
Polymers 2014, 6, 860-872; doi:10.3390/polym6030860 Article OPEN ACCESS polymers ISSN 2073-4360 www.mdpi.com/journal/polymers Living Radical Polymerization via Organic Superbase Catalysis Lin Lei, Miho
More information