Investigating Nitroxide-Mediated Radical Polymerization of Styrene over a Range of Reaction Conditions
|
|
- Ella McDowell
- 5 years ago
- Views:
Transcription
1 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 University of Waterloo 1
2 Controlled Radical Polymerization (CRP) (Co) polymers with precisely controlled architectures Living Ionic Polymerization (good control but stringent conditions; relatively small number of monomers) Regular radical polymerization ( versatile reaction conditions but poor control over some polymer characteristics) 2
3 Controlled Radical Polymerization (CRP) Regular Radical Polymerization Controlled Radical Polymerization Living Ionic Polymerization 3
4 Controlled Radical Polymerization (CRP) Examples of molecular structures attained 4
5 Controlled Radical Polymerization (CRP) Applications Acrylic block copolymers as stabilizers in coating, ink applications Additives suitable for use as components of lubricating oils ABC type block copolymers 5
6 Controlled Radical Polymerization (CRP) Nitroxide- Mediated Radical Polymerization (NMRP) R Atom Transfer Radical Polymerization (ATRP) R Br + CuBr (L) R Reversible Addition-Fragmentation Transfer (RAFT) R m S C S TEMP K a K d K a K d R + TEMP + CuBr 2 (L) + + R R S C S R n K exch m n z z 6
7 Controlled Radical Polymerization (CRP) R + X R X (Active) K deact K act (Dormant) Exchange equilibrium favours dormant species Concentration of radicals is low; bimolecular termination almost negligible Radicals grow at the same average rate; low polydispersity product 7
8 Controlled Radical Polymerization (CRP) Prerequisites Small contribution of chain breaking reactions (termination and transfer reactions) Fast initiation compared to propagation Fast exchange between active and dormant species (provides uniformity in chain length) 8
9 Controlled Radical Polymerization (CRP) ln([m]0/[m]) slow initiation living state termination M n time FRP LRP conversion Deviation from linearity can result from slow initiation or loss of radicals by termination 9
10 Nitroxide-Mediated Radical Polymerization (NMRP) Addition of a stable nitroxide radical, able to trap the propagating radical in a thermally unstable species The most common nitroxide used as trapping agent is TEMP (2, 2, 6, 6 tetramethyl-1-piperidinyloxy) 10
11 NMRP of Styrene with BP and TEMP + STY Initiator efficiency factor (f) k i Initiation (Thermal) Self initiation of Styrene Benzoyl Peroxide Benzoyloxy radical 2 C 11
12 NMRP of Styrene with BP and TEMP C n + n C + N TEMP k p Propagation k deact k act x n C N K = k deact / k act 12
13 Side Reactions Reaction between TEMP and BP N C Nitroxide decomposition C N + 13
14 Uncertain Aspects (?) Initiator efficiency factor (f) Uncertain kinetic constants Side reactions 14
15 bjectives Clarify the effect of polymerization conditions (TEMP/ BP ratio and temperature ) Conversion (rate) Molecular weights Polydispersity Generate a source of reliable experimental data Validation of mathematical models Parameter estimation Identification of optimal polymerization conditions 15
16 Summary of Runs Temperature ( C) [BP] 0 M Nil Nil Nil [TEMP] / [BP] Replicate Remarks Styrene with unimolecular initiator + Replicate + Replicate Thermal (self) initiation of styrene + Replicate - Styrene with TEMP only 16
17 Effect of TEMP/BP Ratio Conversion, X TEMP/BP=0.9 TEMP/BP = 1.1 TEMP/BP=1.1,Independent replicate TEMP/BP = 1.2 TEMP/BP = Time, t (hr) STY polymerization at 120 C, [BP] 0 = M 17
18 Weight Average Molecular Weight (gr/mol) 40,000 35,000 30,000 25,000 20,000 15,000 10,000 5, Conversion, X TEMP/BP=0.9 TEMP/BP=1.1 TEMP/BP=1.2 TEMP/BP=1.5 STY polymerization at 120º C, [BP] 0 = M 18
19 Polydispersity, PDI TEMP/BP=0.9 TEMP/BP=1.1 TEMP/BP=1.2 TEMP/BP= Conversion,X STY polymerization at 120º C, [BP] 0 = M 19
20 bservations The larger the TEMP/ BP ratio (the more TEMP in the recipe), the slower the polymerization Higher values of average molecular weights, Mn and Mw, are obtained as TEMP/BP ratio decreases Low PDI values, below 1.2 Similar trends with experimental data at 130 C (not shown) 20
21 Effect of Temperature Conversion, X Time, t (hr) STY polymerization at TEMP / BP =
22 Weight Average Molecular Weight (gr/mol) PDI 40,000 35,000 30,000 25,000 20,000 15,000 10,000 5, T = 130 T = 120 T = 120,Independent replicate Conversion, X STY polymerization at TEMP / BP =
23 Mathematical Modeling Kinetic model based on a detailed reaction mechanism Molar balances; population balances; set of ordinary differential equations General trends K Satisfactory prediction of experimental data but more work needs to be done ( fine-tuning of key but uncertain parameters) 23
24 Concluding Remarks ptimal ratio to achieve lowest polydispersity seems to be around [TEMP]/ [BP] = 1.2 There is no pronounced temperature effect at studied conditions Model trends and preliminary predictions satisfactory for typical polymerization variables (on going work) PDI TEMP/BP Ratio 24
25 Future Steps Experimental : Comparison with unimolecular initiator Different initiator (tetrafunctional vs. monofunctional initiator) Modeling : More rigorous parameter estimation Using Bayesian design to guide our experimentation for better understanding of the reaction mechanism 25
26 Acknowledgements NSERC CR Grant GSST MNVA Solutions Canada Research Chair (CRC) program ( A. Penlidis) CR grant is a collaborative effort under an Inter - American Materials Collaboration ( IAMC ) joint project with Prof. E. Vivaldo-Lima, M. Roa-Luna ( UNAM, Mexico ) and Prof. L. M.F. Lona, J.B. Ximenes ( Campinas, Brazil ) 26
27 27
28 References Handbook of Radical Polymerization. Matyjaszewski, K., and Davis, T.P., Eds. Wiley-Interscience: Hoboken, Georges, M.K., Veregin, R.P.N., Kazmaier, P.M., and Hamer, G.K. (1993) Macromolecules, 26 (11): Greszta, D. and Matyjaszewski, K. (1996) Macromolecules, 29: MacLeod, P. J., Veregin R.P.N., dell, P.G., and Georges, M.K. (1997) Macromolecules, 30 : Bonilla, J., Saldívar, E., Flores-Tlacuahuac, A., Vivaldo-Lima, E., Pfaendner, R., and Tiscareño-Lechuga, F. (2002) Polym. React. Eng. J., 10 (4): Goto, A. and Fukuda, T. (2004) Prog. Polym. Sci., 29: Roa- Luna, M., Nabifar, A., Diaz-Barber, M. P., McManus, N.T., Vivaldo- Lima, E., Lona, L.M.F., and Penlidis, A. (2007) J. Macromol. Sci., A: Pure Appl. Chem., A44:
29 CH 2 CH CH 2 CH n N k decomp CH 2 CH CH CH H N n + 29
30 Experimental Polymerization Ampoules (~ 4ml volume): degassed, torch-sealed, and then placed in liquid nitrogen until used Isothermal oil bath Polymer Characterization Monomer conversion Gravimetry Molecular weight averages and polydispersity Gel permeation chromatography (GPC) 30
31 Conversion, X Results Replicate Time, t (hr) Ln [M]0/[M] Time, t (hr) STY polymerization at 120 C, TEMP/BP =
32 Average Molecular Weights (gr/mol) PDI 30,000 25,000 20,000 15,000 10,000 5, Mn Mw Conversion, X STY polymerization at 120 C, TEMP/BP =
33 Remarks As expected, polymerization proceeds faster at the higher temperature After about 80-85% conversion, rates are almost identical for both temperatures A small reduction in molecular weight values as temperature increases Experimental data also available for TEMP/ BP=1.1 33
34 Mathematical Modeling 1 Conversion, X Experimental data 0.1 Predicted Profile Time, t (hr) Number Average Molecular Weight (g/mol) Experimental data Predicted Profile Conversion, X STY polymerization at T = 130 C,TEMP/BP =
35 PDI Predicted Experimental data Profile Conversion, X STY polymerization at T = 130 C,TEMP/BP =
36 0.024 Concentration, mol/l [I] [Nx*] [Ne] 0 1.E-10 1.E-09 1.E-08 1.E-07 1.E-06 1.E-05 1.E-04 1.E-03 1.E-02 1.E-01 1.E+00 1.E+01 1.E+02 Time (hr) Typical calculated profiles for concentration of initiator, nitroxyl stable radicals and alcoxyamine 36
37 Description Step Chemical initiation I k d 2R in 2 Nitroxyl ether decomposition k a N R + N E k in x d 2 Kinetic Mechanism (Bonilla et al., 2002) Mayo dimerization Thermal initiation First propagation (primary radicals) k dim M + M D M D D M i + k a + k p R + M R First propagation (monomeric radicals) k M + M p R1 First propagation (dimeric radicals) k D + M p R1 Propagation Dormant living exchange (monomeric alkoxyamine) Dormant living exchange (polymeric alkoxyamine) in r k p R + M R k a M + N MN x kda k a R + N R N r x k r x da k Alkoxyamine decomposition MN decomp M + HN Rate enhancement reaction 3 D+ N k h D + HN Termination by combination x x R + R P + k tc r s r s r x x x Termination by disproportionation Transfer to monomer Transfer to dimer R + R P + P r k td r s r s k fm R + M P + M r k fd R + D P + D r r 37
38 Description Step Chemical initiation I k d 2R in 2 Nitroxyl ether decomposition k a N R + N E k in x d 2 Kinetic Mechanism (Bonilla et al., 2002) Mayo dimerization Thermal initiation First propagation (primary radicals) k dim M + M D M D D M i + k a + k p R + M R First propagation (monomeric radicals) k M + M p R1 First propagation (dimeric radicals) k D + M p R1 Propagation Dormant living exchange (monomeric alkoxyamine) Dormant living exchange (polymeric alkoxyamine) in r k p R + M R k a M + N MN x kda k a R + N R N r x k r x da k Alkoxyamine decomposition MN decomp M + HN Rate enhancement reaction 3 D+ N k h D + HN Termination by combination x x R + R P + k tc r s r s r x x x Termination by disproportionation Transfer to monomer Transfer to dimer R + R P + P r k td r s r s k fm R + M P + M r k fd R + D P + D r r 38
39 Thermal Self initiation of Styrene 39
40 40
MODELING 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 informationAN ALTERNATIVE ROUTE TO PRODUCE STANDARDS FOR GEL PERMEATION CHROMATOGRAPHY USING NITROXIDE MEDIATED POLYMERIZATION
Brazilian Journal of Chemical Engineering ISSN 0104-6632 Printed in Brazil www.abeq.org.br/bjche Vol. 34, No. 01, pp. 283-293, January - March, 2017 dx.doi.org/10.1590/0104-6632.20170341s20150547 AN ALTERNATIVE
More informationSS 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 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 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 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 informationRadical Polymerizations II Special Cases
Radical Polymerizations II pecial Cases Devon A. hipp Department of Chemistry, & Center for Advanced Materials Processing Clarkson University Potsdam, NY 13699-5810 Tel. (315) 268-2393, Fax (315) 268-6610
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 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 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 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 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 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 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 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 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 informationLiving Radical Copolymerization of Styrene/Maleic Anhydride
Living Radical Copolymerization of Styrene/Maleic Anhydride EUN-SOO PARK, 1 MAL-NAM KIM, 3 IK-MO LEE, 2 HAN SUP LEE, 1 JIN-SAN YOON 1 1 Department of Applied Chemistry, Inha University, 402-751 Inchon,
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 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 informationControlled grafting of poly(styrene-ran-n-butyl methacrylate) to isotactic polypropylene with nitroxidemediated
e-polymers 2003, no. 007. http://www.e-polymers.org ISSN 1618-7229 Controlled grafting of poly(styrene-ran-n-butyl methacrylate) to isotactic polypropylene with nitroxidemediated polymerization Yusuke
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 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 informationSUPPORTING INFORMATION
SUPPORTING INFORMATION Optimizing The Generation Of Narrow Polydispersity ArmFirst Star Polymers Made Using RAFT Polymerization Julien Ferrera, a Jay Syrett, b Michael Whittaker, a David Haddleton, b Thomas
More informationIncubation Period in the 2,2,4,4-Tetramethyl-1- piperidinyloxy-mediated Thermal Autopolymerization of Styrene: Kinetics and Simulations
Incubation Period in the 2,2,4,4-Tetramethyl-1- piperidinyloxy-mediated Thermal Autopolymerization of Styrene: Kinetics and Simulations ENRIQUE SALDÍVAR-GUERRA, 1 JOSÉ BONILLA, 1 GREGORIO ZACAHUA, 2 MARTHA
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 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 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 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 informationSynthesis of Arborescent Polybutadiene. Ala Alturk and Mario Gauthier, IPR Symposium, University of Waterloo, N2L 3G1 Canada
Synthesis of Arborescent Polybutadiene Ala Alturk and Mario Gauthier, IPR Symposium, University of Waterloo, N2L 3G1 anada Arborescent polymers are characterized by a tree-like architecture and a high
More informationPolymer Reaction Engineering Issues About Polymerization in Supercritical Carbon Dioxide
UNIVERSIDAD NACIONAL AUTÓNOMA DE MÉXICO UNIVERSITY OF WATERLOO Polymer Reaction Engineering Issues About Polymerization in Supercritical Carbon Dioxide Dr. Eduardo Vivaldo-Lima Professor (UNAM), National
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 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 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 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 informationof Polystyrene 4-arm Stars Synthesized by RAFT- Mediated Miniemulsions.
Supporting Information to Narrow Molecular Weight and Particle Size Distributions of Polystyrene 4-arm Stars Synthesized by RAFT- Mediated Miniemulsions. Hazit A. Zayas, Nghia P. Truong, David Valade,
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 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 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 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 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 informationHIV anti-latency treatment mediated by macromolecular prodrugs of histone deacetylase inhibitor, panobinostat
Electronic Supplementary Material (ESI) for Chemical Science. This journal is The Royal Society of Chemistry 206 Supporting information HIV anti-latency treatment mediated by macromolecular prodrugs of
More informationSupporting Information. Nitroxide Mediated Polymerization of methacrylates at moderate temperature
Supporting Information Nitroxide Mediated Polymerization of methacrylates at moderate temperature Christophe Detrembleur, Christine Jérôme, Julien De Winter, Pascal Gerbaux, Jean-Louis Clément, Yohann
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 informationSegmented Copolymers. Segmented Polyurethanes (Prof. Hammond s thesis)
0.569 Synthesis of Polymers Prof. Paula ammond Lecture 0: Introduction to Radical Polymerization Segmented opolymers Segmented Polyurethanes (Prof. ammond s thesis) soft segment ends in groups - oligomer
More informationPolymeric Palladium-Mediated Carbene Polymerization
Electronic Supplementary Material (ESI) for Polymer Chemistry. This journal is The Royal Society of Chemistry 2015 Supporting Information for Polymeric Palladium-Mediated Carbene Polymerization Feifei
More informationSupplementary Information. "On-demand" control of thermoresponsive properties of poly(n-isopropylacrylamide) with cucurbit[8]uril host-guest complexes
upplementary Information "n-demand" control of thermoresponsive properties of poly(n-isopropylacrylamide) with cucurbit[8]uril host-guest complexes Urs Rauwald, Jesús del Barrio, Xian Jun Loh, and ren
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 informationComparative Study of Reactivity Ratio Estimation based on Composition Data at. Various Conversion Levels in Binary and Ternary Polymerization Systems
Comparative Study of Reactivity Ratio Estimation based on Composition Data at Various Conversion Levels in Binary and Ternary Polymerization Systems Niousha Kazemi, Tom Duever, and Alex Penlidis Institute
More informationChapter 4 Copolymerization
Chapter 4 Copolymerization 4.1 Kinetics of Copolymerization 4.1.1 Involved Chemical Reactions Initiation I 2 + M 2R 1 r = 2 fk d I 2 R I Propagation Chain Transfer Termination m,n + k p m+1,n m,n + B k
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 informationSOLUTION STYRENE POLYMERIZATION IN A MILLIREACTOR
SOLUTION STYRENE POLYMERIZATION IN A MILLIREACTOR L. FULLIN 1, E. MELLONI 1 and A.S. VIANNA Jr 1 1 Universidade de São Paulo, Departamento de Engenharia Química E-mail for contact: ardson@usp.br ABSTRACT
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 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 informationControlled free radical polymerization of styrene initiated by a [BPO-polystyrene-(4-acetamido-TEMPO)] macroinitiator
Die Angewandte Makromolekulare Chemie 265 (1999) 69 74 (Nr. 4630) 69 Controlled free radical polymerization of styrene initiated by a [BPO-polystyrene-(4-acetamido-TEMPO)] macroinitiator Chang Hun Han,
More informationSupporting Information
Supporting Information UCST or LCST? Composition-Dependent Thermoresponsive Behavior of Poly(N-Acryloylglycinamide-co-Diacetone Acrylamide) Wenhui Sun, Zesheng An*, Peiyi Wu * Experimental Materials Glycinamide
More informationMS received 1 December 2012; revised 22 February 2013; accepted 15 April 2013
J. Chem. Sci. Vol. 12, No. 4, July 2013, pp. 791 797. c Indian Academy of Sciences. Synthesis and characterization of poly(2-ethylhexyl acrylate) prepared via atom transfer radical polymerization, reverse
More informationMEASUREMENT OF THE CHAIN TRANSFER CONSTANT FOR THE POLYMERIZATION OF STYRENE USING D-LIMONENE AS RENEWABLE CTA
MEASUREMENT OF THE CHAIN TRANSFER CONSTANT FOR THE POLYMERIZATION OF STYRENE USING D-LIMONENE AS RENEWABLE CTA Rodrigo Schlischting 1, Ricardo A. F. Machado 2, Pedro H. H. de Araújo 2, Johan P. A. Heuts
More informationFormation Rate Constants of the Mayo Dimer in the Autopolymerization of Styrene
RAPID COMMUNICATION Formation Rate Constants of the Mayo Dimer in the Autopolymerization of Styrene THOMAS KOTHE, HANNS FISCHER Physikalisch-Chemisches Institut der Universitaet Zuerich, Winterthurerstrasse
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 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 informationAccessory Publication
10.1071/CH10127_AC CSIRO 2010 Australian Journal of Chemistry 2010, 63(8), 1210 1218 Accessory Publication Synthesis of Core Shell Nanoparticles with Polystyrene Core and PEO Corona from Core-Crosslinked
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 informationControlled Structure Polymer Latex by Nitroxide-Mediated Polymerization. Jason S. Ness, Arkema Inc., USA Stéphanie Magnet, Arkema, France
Controlled Structure Polymer Latex by Nitroxide-Mediated Polymerization Jason S. Ness, Arkema Inc., USA Stéphanie Magnet, Arkema, France Introduction Free radical emulsion polymerization is commonly employed
More informationA Kinetic Monte Carlo Study on the Nucleation Mechanisms of Oil-Soluble Initiators in the Miniemulsion Polymerization of Styrene
A Kinetic Monte Carlo Study on the Nucleation Mechanisms of Oil-Soluble Initiators in the Miniemulsion Polymerization of Styrene JONATHAN A. RAWLSTON, 1 JUCHEN GUO, 2 F. JOSEPH SCHORK, 2 MARTHA A. GROVER
More informationStudy of the thermo-oxidative degradation behavior of isotactic polypropylene with the varying ethylene content
Indian Journal of Chemistry Vol. 46B, July 2007, pp. 1198-1202 Note Study of the thermo-oxidative degradation behavior of isotactic polypropylene with the varying ethylene content M S Alam*, S M Abdur
More informationXiangxiong Chen, Mohd Yusuf Khan and Seok Kyun Noh* School of Chemical Engineering, Yeungnam University, Dae-dong, Gyeongsan,
Electronic Supplementary Information For M Amount of Fe (III)-mediated ATR of MMA with hosphorus Containing Ligands in the Absence of Any Additives Xiangxiong Chen, Mohd Yusuf Khan and Seok Kyun Noh* School
More informationPolystyrene-block-poly(butyl acrylate) and polystyreneblock-poly[(butyl
Macromol. Rapid Commun. 2000, 21, 921 926 921 Communication: Polystyrene-block-poly(butyl acrylate) and polystyrene-block-poly[(butyl acrylate)-co-styrene] block copolymers were prepared in an aqueous
More informationSUPPLEMENTARY INFORMATION
DOI: 10.1038/NCHEM.2633 Mechanically controlled radical polymerization initiated by ultrasound Hemakesh Mohapatra, Maya Kleiman, Aaron P. Esser-Kahn Contents 1. Materials and methods 2 2. Procedure for
More informationSupporting Information
Electronic Supplementary Material (ESI) for ChemComm. This journal is The Royal Society of Chemistry 2014 Supporting Information Nanoparticle-to-vesicle and nanoparticle-to-toroid transitions of ph-sensitive
More informationEffect of Feed Rate on Structure of Hyperbranched Polymers Formed by Self-Condensing Vinyl Polymerization in Semibatch Reactor
8252 Macromolecules 2005, 38, 8252-8257 Effect of Feed Rate on Structure of Hyperbranched Polymers Formed by Self-Condensing Vinyl Polymerization in Semibatch Reactor Kuo-Chung Cheng,*, Tsu-Hwang Chuang,
More informationEngineering aspect of emulsion polymerization
Engineering aspect of emulsion polymerization Joong-In Kim Bayer Corp., Plastics, Technology Yonsei University Contents Free radical polymerization kinetics Emulsion polymerization Reactor configuration
More informationLecture 27 More Polymers
Lecture 27 More Polymers Step Chain April 25, 2018 Where: MEZ 1.306!! Final Exam When: Friday, May 11 th, 2:00 5:00 PM Do: Study lecture notes, homework, reading Practice: Hydrolysis, signatures and synthesis.
More informationPhoto-Cleavage of Cobalt-Carbon Bond: Visible. Light-Induced Living Radical Polymerization Mediated by. Organo-Cobalt Porphyrins
Photo-Cleavage of Cobalt-Carbon Bond: Visible Light-Induced Living Radical Polymerization Mediated by Organo-Cobalt Porphyrins Yaguang Zhao, Mengmeng Yu, and Xuefeng Fu* Beijing National Laboratory for
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 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 informationPCE WITH WELL-DEFINED STRUCTURES AS POWERFUL CONCRETE SUPERPLASTICIZERS FOR ALKALI-ACTIVATED BINDERS
PCE WITH WELL-DEFINED STRUCTURES AS POWERFUL CONCRETE SUPERPLASTICIZERS FOR ALKALI-ACTIVATED BINDERS 2 ND INTERNATIONAL CONFERENCE ON POLYCARBOXYLATE SUPERPLASTICIZERS 28. SEPTEMBER 2017 SIKA TECHNOLOGY
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 informationPolymerization of Isoprene by Using Benzyl Diethyldithiocarbamate as an Iniferter
RESEARH ARTILE ScienceAsia 5 (999) : 35-4 Polymerization of Isoprene by Using Benzyl Diethyldithiocarbamate as an Iniferter A Kongkaew a,b and J Wootthikanokkhan a,* a Division of Materials Technology,
More informationQuiz 5 Introduction to Polymers
100506 Quiz 5 Introduction to Polymers 1) Polyurethane in the video shown in class is formed from two liquids that are mixed. After mixing the solution foams and expands fairly rapidly forming a solid
More informationScope and Limitations of the Nitroxide-Mediated Radical Ring Opening Polymerization of Cyclic Ketene Acetals
Electronic Supporting Information for Scope and Limitations of the Nitroxide-Mediated Radical Ring Opening Polymerization of Cyclic Ketene Acetals Antoine Tardy, a Vianney Delplace, b Didier Siri, a Catherine
More informationFinal Exam, May 6, 2011, 200 pts Polymer Chemistry, CHEM 466, Spring 2011 Texas A&M University, College Station, TX, USA
On my honor, as an Aggie, I have neither given nor received unauthorized aid on this academic work. Final Exam, May 6, 2011, 200 pts Polymer Chemistry, CHEM 466, Spring 2011 Texas A&M University, College
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 informationLiving Cationic Polymerization of p-alkoxystyrenes by Free Ionic Species
Living Cationic Polymerization of p-alkoxystyrenes by Free Ionic Species SHOKYOKU KANAOKA, TOSHINOBU HIGASHIMURA Department of Materials Science, School of Engineering, The University of Shiga Prefecture,
More informationHow fast reactants turn into products. Usually measured in Molarity per second units. Kinetics
How fast reactants turn into products. Usually measured in Molarity per second units. Kinetics Reaction rated are fractions of a second for fireworks to explode. Reaction Rates takes years for a metal
More informationInvestigation of Nitroxide Radical Coupling Reaction in Wide Temperature Range and Different Catalyst System
Investigation of Nitroxide Radical Coupling Reaction in Wide Temperature Range and Different Catalyst System WENCHENG LIN, BING HUANG, QIANG FU, GUOWEI WANG, JUNLIAN HUANG Department of Macromolecular
More informationSupporting Information
Electronic Supplementary Material (ESI) for ChemComm. This journal is The Royal Society of Chemistry 2014 Supporting Information Synthesis of Poly(dihydroxystyrene-block-styrene) (PDHSt-b-PSt) by the RAFT
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 informationR package: HomoPolymer
R package: HomoPolymer User Manual Gianmarco Polotti January 8, 2015 1 Package Structure The package structure with links among interconnected functions are shown below. The software may run either interactively
More informationSUPPORTING INFORMATION
SUPPORTING INFORMATION Polymerization-induced Self-Assembly of Homopolymer and Diblock copolymer: A Facile Approach for preparing Polymer Nano-objects with Higher Order Morphologies Jianbo Tan *a,b, Chundong
More informationKinetics of Self-Condensing Vinyl Hyperbranched Polymerization in Three-Dimensional Space
Kinetics of Self-Condensing Vinyl Hyperbranched Polymerization in Three-Dimensional Space XUEHAO HE, JING TANG Department of Polymer Science and Engineering, School of Chemical Engineering and Technology,
More informationThe Influence of RAFT on the Rates and Molecular Weight Distributions of Styrene in Seeded Emulsion Polymerizations
The Influence of RAFT on the Rates and Molecular Weight Distributions of Styrene in Seeded Emulsion Polymerizations MICHAEL J. MONTEIRO, MARCELLE HODGSON, HANS DE BROUWER Department of Polymer Chemistry
More informationTEMPO-controlled free radical suspension polymerization
62 Die Angewane Makromolekulare Chemie 265 (1999) 62 68 (Nr. 4629) TEMPO-controlled free radical suspension polymerization Gudrun Schmi-Naake*, Marco Drache, Carsten Taube Institut für Technische Chemie,
More informationBlock copolymers containing organic semiconductor segments by RAFT polymerization
Block copolymers containing organic semiconductor segments by RAFT polymerization Ming Chen, Matthias Häussler, Graeme Moad, Ezio Rizzardo Supplementary Material Radical polymerizations in the presence
More informationPolymerization Induced Self-Assembly: Tuning of Nano-Object Morphology by Use of CO 2
Electronic Supplementary Material (ESI) for Polymer Chemistry. This journal is The Royal Society of Chemistry 2015 SUPPORTING INFORMATION Polymerization Induced Self-Assembly: Tuning of Nano-Object Morphology
More informationEngineering Polymers for Organic Photovoltaics
Engineering Polymers for rganic Photovoltaics by Elijah Bultz A document submitted in partial fulfillment of the degree Masters of Applied Science. Department of Chemical Engineering and Applied Chemistry
More informationPost-Polymerization. . macromolecule (1) While dying, macro-radicals react with the monomer: k p R n + M Rn+1 (2)
Post-Polymerization Technical Paper By Igor V Khudyakov, PhD, DSc UV-curing technology is often selected because of the highspeed nature of the process Although curing is initiated by UV irradiation, polymerization
More informationSupporting Online Material for
www.sciencemag.org/cgi/content/full/332/6025/81/dc1 Supporting Online Material for Electrochemically Mediated Atom Transfer Radical Polymerization Andrew J. D. Magenau, Nicholas C. Strandwitz, Armando
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 informationMATHEMATICAL SIMULATION OF THE STYRENE- BUTADIENE RUBBER S PRODUCTION IN THE CASCADE OF REACTORS BY THE MONTE CARLO METHOD
Int. J. Chem. Sci.: 4(4), 206, 865-876 ISSN 0972-768X www.sadgurupublications.com MATHEMATICAL SIMULATION OF THE STYRENE- BUTADIENE RUBBER S PRODUCTION IN THE CASCADE OF REACTORS BY THE MONTE CARLO METHOD
More informationSupplementary Information
Supplementary Information Self-assembly of Metal-Polymer Analogues of Amphiphilic Triblock Copolymers 1 Zhihong Nie, 1 Daniele Fava, 1, 2, 3 Eugenia Kumacheva 1 Department of Chemistry, University of Toronto,
More information