Simultaneous Continuous, Nonchromatographic Monitoring and Discrete Chromatographic Monitoring of Polymerization Reactions

被引:8
作者
Alb, Alina M. [1 ]
Drenski, Michael F. [1 ]
Reed, Wayne F. [1 ]
机构
[1] Tulane Univ, Tulane Ctr Polymer React Monitoring & Characteriz, New Orleans, LA 70118 USA
关键词
gel permeation chromatography (GPC); kinetics (polym.); light scattering; living polymerization; molecular weight distribution/molar; SIZE-EXCLUSION CHROMATOGRAPHY; FREE-RADICAL POLYMERIZATION; NEAR-INFRARED SPECTROSCOPY; INTRAMOLECULAR CHAIN TRANSFER; PROPAGATION RATE COEFFICIENT; PULSED-LASER POLYMERIZATION; BUTYL ACRYLATE; EMULSION COPOLYMERIZATION; RAMAN-SPECTROSCOPY; MOLAR-MASS;
D O I
10.1002/app.29501
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
Automatic continuous nonchromatographic monitoring and discrete chromatographic monitoring were Coupled together for the first time and used to monitor free radical and controlled-radical polymerization reactions. This was achieved by adding a multidetector Size Exclusion Chromatogaphy (SEC) system (alternatively termed Gel Permeation Chromatography, GPC) to the ACOMP platform (Automatic Continuous Online Monitoring of Polymerization reactions). The fact that the reactor solution is already preconditioned in the ACOMP front-end to the concentration levels used in SEC makes direct coupling possible. Kinetics from two different types of reactions, Reversible Addition Fragmentation Transfer (RAFT) and free radical polymerization of butyl acrylate W(were studied, including the production of a bimodal population. Complementary and contrasting features from the continuous and SEC approaches are highlighted. The main advantage of the SEC detection is to follow the evolution Of full molecular weight distributions (MWD), especially in 'living' type reactions, where polydispersity decreases with monomer conversion, whereas the continuous detection provides a much more detailed characterization of the reaction. Interestingly, in the case where a bimodal molecular weight distribution was produced, the continuous method automatically detected the Onset of the second mode in a model independent fashion, whereas SEC could only discern the bimodality by applying preconceived models. The SEC approach will have valuable niche applications, however, such as when reactions are relatively slow, monitoring narrow polydispersity is of primary importance, and also in copolymerization and terpolymerization reactions where complex mixtures of reagents (e.g., RAFT agents, copper ions, etc.) make unfractionated spectroscopic resolution of comonomers difficult. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 113: 190-198, 2009
引用
收藏
页码:190 / 198
页数:9
相关论文
共 33 条
[1]   Chain transfer to polymer in free-radical solution polymerization of n-butyl acrylate studied by NMR spectroscopy [J].
Ahmad, NM ;
Heatley, F ;
Lovell, PA .
MACROMOLECULES, 1998, 31 (09) :2822-2827
[2]   Simultaneous monitoring of polymer and particle characteristics during emulsion polymerization [J].
Alb, Alina M. ;
Reed, Wayne F. .
MACROMOLECULES, 2008, 41 (07) :2406-2414
[3]   Automatic continuous online monitoring of polymerization reactions (ACOMP) [J].
Alb, Alina M. ;
Drenski, Michael F. ;
Reed, Wayne F. .
POLYMER INTERNATIONAL, 2008, 57 (03) :390-396
[4]   Kinetic trends in RAFT homopolymerization from Online monitoring [J].
Alb, Alina M. ;
Serelis, Algirdas K. ;
Reed, Wayne F. .
MACROMOLECULES, 2008, 41 (02) :332-338
[5]   Quantitative contrasts in the copolymerization of acrylate- and methacrylate-based comonomers [J].
Alb, Alina M. ;
Enohnyaket, Pascal ;
Drenski, Michael F. ;
Shunmugam, Raja ;
Tew, Gregory N. ;
Reed, Wayne F. .
MACROMOLECULES, 2006, 39 (24) :8283-8292
[6]   Online monitoring of copolymerization involving comonomers of similar spectral characteristics [J].
Alb, Alina M. ;
Enohnyaket, Pascal ;
Drenski, Michael F. ;
Head, Aaron ;
Reed, Alex W. ;
Reed, Wayne F. .
MACROMOLECULES, 2006, 39 (17) :5705-5713
[7]   Critically evaluated rate coefficients for free-radical polymerization, 5 - Propagation rate coefficient for butyl acrylate [J].
Asua, JM ;
Beuermann, S ;
Buback, M ;
Castignolles, P ;
Charleux, B ;
Gilbert, RG ;
Hutchinson, RA ;
Leiza, JR ;
Nikitin, AN ;
Vairon, JP ;
van Herk, AM .
MACROMOLECULAR CHEMISTRY AND PHYSICS, 2004, 205 (16) :2151-2160
[8]  
CARDENASVALENCI.AM, 2003, ACS SYM SER, P83
[9]   Living free-radical polymerization by reversible addition-fragmentation chain transfer: The RAFT process [J].
Chiefari, J ;
Chong, YK ;
Ercole, F ;
Krstina, J ;
Jeffery, J ;
Le, TPT ;
Mayadunne, RTA ;
Meijs, GF ;
Moad, CL ;
Moad, G ;
Rizzardo, E ;
Thang, SH .
MACROMOLECULES, 1998, 31 (16) :5559-5562
[10]  
Dotson NeilA., 1996, POLYM PROCESS MODELI