Automatic continuous online monitoring of polymerization reactions
||This article may be too technical for most readers to understand. (October 2012)|
Automatic continuous online monitoring of polymerization reactions (ACOMP) is a technique developed at Tulane University by W.F. Reed in 1998, with the first peer-reviewed paper appearing in 1998.
Polymerization reactions are difficult to monitor in real-time, as characteristics and properties of the polymers are often unknown until after the reaction is complete. The ACOMP technique monitors these reactions in real-time by automatically and continuously diluting small streams of polymer out of the reactor and then running the sample though widely accepted detectors to measure such standard parameters as refractive index, light scattering, and intrinsic viscosity, thus characterizing the polymer as the reaction is continuing. " ACOMP can be used as an analytical method during research and development, as a tool for reaction optimization at the bench and pilot plant level and, even for feedback control of full-scale reactors.
The method can determine in a model-independent fashion the evolution of average molar mass and intrinsic viscosity, monomer conversion kinetics and, in the case of copolymers, the average composition drift and distribution; it is a direct measurement, not based on the theoretic understanding of the reaction. ACOMP is applicable in the areas of free radical and controlled radical homo- and copolymerization, polyelectrolyte synthesis, heterogeneous phase reactions, including emulsion polymerization, adaptation to batch and continuous reactors, and modifications of polymers.
ACOMP as a tool for efficiency
ACOMP is envisioned as an energy saving and efficiency optimizing technology for the polymer manufacturing industry. Different reaction parameters such as temperature, pressure, and reagent feeds can be adjusted according to what ACOMP analyzes in real-time, maximizing the efficiency of the reaction and reducing the problem of inconsistent product quality and wasted batches.
The proprietary platform developed by Wayne Reed and coworkers, termed Automatic Continuous Online Monitoring of Polymerization reactions, or ACOMP, has been demonstrated in the laboratory environment since 1998, with over 30 publications in high-impact, peer-reviewed journals. , It has been applied to polycondensation, free radical, controlled radical, other 'living' type reactions, and post-polymerization reactions, such as grafting, etc., and has been applied in solvent, bulk and inhomogeneous phases, such as emulsion and inverse emulsion, and in batch, semi-continuous and continuous reactors.
The ACOMP front-end samples the reactor continuously, producing a dilute sample stream on which yjr multiple analytical measurements are simultaneously and continuously made. These include light scattering, viscosity, refractivity, conductivity, ultra-violet absorption, etc. The types of instruments can be tailored to the specific application. This data yields continuously the derived properties of the amount of reagents converted to polymer, polymer molecular weight, intrinsic viscosity, average composition drift and distribution, and many other properties, and consequently indicates when the reaction is complete, and shows whether there are problems during the reaction, and whether the product is according to specification.
ACOMP is fully proven at the laboratory level, and was commercially available for this use under license from Varian Inc., up until the beginning of 2009. Due to the current financial crisis and massive layoffs, however, Varian Inc. cancelled the license with Tulane for the ACOMP patents, and now PolyRMC is seeking to develop the technology further. Specifically, PolyRMC is looking for potential collaborators for a technology transfer on a non-profit basis through the Center. This would involve preliminary testing to prove the feasibility of adapting the technology to a specific product. It would also involve actual implementation on a larger scale reactor i.e. a pilot reactor or even a full-sized reactor.
The potential for decreasing reaction times by running reactions closer to their thresholds could provide energy savings, and increase output without any further capital investments. Monitoring reactions in real-time can also provide data on the quality of the polymer being produced so that product consistency can be controlled more closely, and finally wasted batches, due to failed polymerizations, can be eliminated. All of these advantages could make ACOMP very cost-advantageous for any end-users of the technology, and help to increase the overall efficiency of the polymer manufacturing sector as a whole. Other potential national or global impact of ACOMP mass-adaptation may include 1) saving petroleum based and other non-renewable resources in polymer production, 2) advances in novel material properties, quality, versatility, yield, and applications which can lead to better energy saving materials, such as light-weight construction and transportation materials, oil recovery polymers, etc., 3) less greenhouse gas emission per pound of product, 4) less chemical contamination of soil, water, air and surrounding communities and 5) enhanced profitability due to efficiency and quality gains, leading to 6) retention and expansion of this manufacturing sector in the US, with its broad spectrum of blue and white collar jobs, and 7) a quantitative basis for evaluating energy efficiency of polymer manufacturing.
- US patent 6052184 and US Patent 6653150, other patents pending
- F. H. Florenzano; R. Strelitzki; W. F. Reed (1998). "Absolute, Online Monitoring of Polymerization Reactions". Macromolecules 31 (21): 7226–7238. Bibcode:1998MaMol..31.7226F. doi:10.1021/ma980876e.
- W. F. Reed (2000). "A Method for Online Determination of Polydispersity during Polymerization Reactions". Macromolecules 33 (19): 7165–7172. Bibcode:2000MaMol..33.7165R. doi:10.1021/ma0006023.
- A. M. Alb; M. F. Drenski; W. F. Reed (2008). "Implications to Industry: Perspective. Automatic continuous online monitoring of polymerization reactions (ACOMP)". Polymer International 57: 390–396. doi:10.1002/pi.2367.
- A. Giz; H. Giz, J. L. Brousseau; A. Alb; W. F. Reed (2001). "Kinetics and Mechanism of Acrylamide Polymerization by Absolute, Online Monitoring of Polymerization Kinetics". Macromolecules 34 (5): 1180–1191. Bibcode:2001MaMol..34.1180G. doi:10.1021/ma000815s.
- W. F. Reed (2000). "Breaking new ground in polymer science with molecular weight analysis". Invited article, American Laboratory 32 (16): 20–25.
- B. Grassl; A. Alb; W. F. Reed (2001). "Free radical transfer rate determination using online polymerization monitoring". Macromol. Chem. Phys. 202 (12): 2518–2524. doi:10.1002/1521-3935(20010801)202:12<2518::AID-MACP2518>3.0.CO;2-X.
- B. Grassl; W. F. Reed (2002). "Online polymerization monitoring in a continuous tank reactor". Macromol. Chem. Phys. 203 (3): 586–597. doi:10.1002/1521-3935(20020201)203:3<586::AID-MACP586>3.0.CO;2-I.
- F. Chauvin; A. M. Alb; D. Bertin; W. F. Reed (2002). "Kinetics and molecular weight evolution during controlled radical polymerization". Macromol.Chem. Phys. 203 (14): 2029–2040. doi:10.1002/1521-3935(200210)203:14<2029::AID-MACP2029>3.0.CO;2-#.
- A. Giz; A. O. Koc; H. Giz; A. Alb; W. F. Reed (2002). "Online monitoring of reactivity ratios, composition, sequence length, and molecular weight distributions during free radical copolymerization". Macromolecules 35 (17): 6557–6571. Bibcode:2002MaMol..35.6557C. doi:10.1021/ma0201983.
- W. F. Reed, "Monitoring Kinetic Processes in Polymer Solutions with Time Dependent Static Light Scattering (TDSLS)", Ch. 12, pp. 131–151, in Scattering Methods for the Investigation of Polymers, J. Kahovec, Ed., Wiley VCH, 2002.
- W. F. Reed; A. M. Alb; E. Mignard; H. Giz; A. Giz; F. H. Florenzano; R. Farinato "Automatic Continuous Online Monitoring of Polymerization Reactions (ACOMP)", Polymeric Materials: Science and Engineering 2003, 88, 476–478.
- E. Mignard; O. Guerret; D. Bertin; W. F. Reed (2003). "Automatic Continuous Online Monitoring of Polymerization Reactions (ACOMP) of High Viscosity Reactions". Polymeric Materials: Science and Engineering 88: 314–316.
- D. Sunbul; H. Catalgil-Giz; W. F. Reed; A. Giz (2004). "An error in variables method for determining the reactivity ratios by on-line monitoring of copolymerization reactions". Macromolecular Theory and Simulation 13 (2): 162–168. doi:10.1002/mats.200300008.
- E. Mignard, T. Leblanc, D. Bertin, O. Guerret, W. F. Reed (2004). "Online monitoring of controlled radical polymerization : Nitroxide mediated gradient copolymerization". Macromolecules 37 (3): 966–975. Bibcode:2004MaMol..37..966M. doi:10.1021/ma035589b.
- W. F. Reed (2004). "Automatic Continuous Online Monitoring of Polymerization reactions (ACOMP)". Feature Article, Polymer News 29 (9): 271–279. doi:10.1080/00323910490981344.
- A. M. Alb; P. Enohnyaket; R. Shunmugam; G. N. Tew; W. F. Reed (2006). "Quantitative contrasts in the copolymerization of acrylate and methacrylate monomers". Macromolecules 39 (24): 8283–8292. Bibcode:2006MaMol..39.8283A. doi:10.1021/ma0616864.
- M. F. Drenski; E. Mignard ; W. F. Reed (2006). "Direct Measurement of Chain Transfer during Controlled Radical Polymerization". Macromolecules 39 (24): 8213–8215. Bibcode:2006MaMol..39.8213D. doi:10.1021/ma061864t.
- A. M. Alb; P. Enohnyaket; J. F. Craymer; T. Eren; E. B. Coughlin, W. F. Reed (2007). "Online monitoring of Ring Opening Metathesis Polymerization of Cyclooctadiene and a Functionalized Norbornene". Macromolecules 40 (3): 444–451. Bibcode:2007MaMol..40..444A. doi:10.1021/ma062241i.
- A. M. Alb; A. Paril; H. Çatalgil-Giz; A. Giz; W. F. Reed (2007). "Evolution of composition, molar mass, and conductivity during the free radical copolymerization of polyelectrolytes". J. Phys. Chem. B 111 (29): 8560–8566. doi:10.1021/jp0688299. PMID 17441756.
- A. Paril; A. M. Alb; W. F. Reed (2007). "Online Monitoring of the Evolution of Polyelectrolyte Characteristics during Postpolymerization Modification Processes". Macromolecules 40 (13): 4409–4413. Bibcode:2007MaMol..40.4409P. doi:10.1021/ma070291x.
- A. M. Alb; A. K. Serelis; W. F. Reed (2008). "Kinetic trends in RAFT homopolymerization from online monitoring". Macromolecules 41 (2).