Automatic, simultaneous control of polymer composition and molecular weight during free radical copolymer synthesis

McAfee, Terry; Montgomery, Rick D.; Zekoski, Thomas; Wu, Aide; Reed, Wayne F.

doi:10.1016/j.polymer.2017.12.005

Title: Automatic, simultaneous control of polymer composition and molecular weight during free radical copolymer synthesis

Abstract

Fully automatic, simultaneous control of polymer composition and molecular weight trajectories during free radical copolymer synthesis was achieved by coupling the continuous ACOMP data stream into a feedback controller which operated pumps for reactor feed of comonomers. The controller operates without recourse to a detailed kinetic model or reactivity ratios. Rather, it uses the fact that instantaneous copolymer chain composition is related to the instantaneous rate of consumption of comonomers, and the rate for each of these is described by rates α₁ and α₂ for comonomers 1 and 2, respectively. The instantaneous weight average molecular weight M_w,inst is proportional to total comonomer concentration via a constant p. Hence, target trajectories for composition and M_w can be independently prescribed and followed. Finally, since α₁, α₂ and p are directly measurable from the ACOMP data stream, their values can be constantly updated by the automatic controller during the reaction process to insure the target trajectories are followed.

Authors:

McAfee, Terry ^[1]; Montgomery, Rick D. ^[2]; Zekoski, Thomas ^[1]; Wu, Aide ^[1]; Reed, Wayne F. ^[1]

Tulane Univ., New Orleans, LA (United States)
Fluence Analytics, New Orleans, LA (United States)

Publication Date:: Thu Dec 21 00:00:00 EST 2017

Research Org.:: Tulane Univ., New Orleans, LA (United States)

Sponsoring Org.:: USDOE Office of Energy Efficiency and Renewable Energy (EERE)

OSTI Identifier:: 1538758

Alternate Identifier(s):: OSTI ID: 1693668

Grant/Contract Number:: EE0005776

Resource Type:: Accepted Manuscript

Journal Name:: Polymer

Additional Journal Information:: Journal Volume: 136; Journal Issue: C; Journal ID: ISSN 0032-3861

Publisher:: Elsevier

Country of Publication:: United States

Language:: English

Subject:: 36 MATERIALS SCIENCE; Polymer science; Automatic polymerization reaction control; Free radical copolymerization; Light scattering; Copolymer composition control; Simultaneous molecular weight; Composition control

Citation Formats


                    McAfee, Terry, Montgomery, Rick D., Zekoski, Thomas, Wu, Aide, and Reed, Wayne F. Automatic, simultaneous control of polymer composition and molecular weight during free radical copolymer synthesis.  United States: N. p., 2017. 
Web.  doi:10.1016/j.polymer.2017.12.005.

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                    McAfee, Terry, Montgomery, Rick D., Zekoski, Thomas, Wu, Aide, & Reed, Wayne F. Automatic, simultaneous control of polymer composition and molecular weight during free radical copolymer synthesis.  United States.  https://doi.org/10.1016/j.polymer.2017.12.005

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                    McAfee, Terry, Montgomery, Rick D., Zekoski, Thomas, Wu, Aide, and Reed, Wayne F. Thu .  
"Automatic, simultaneous control of polymer composition and molecular weight during free radical copolymer synthesis".  United States.  https://doi.org/10.1016/j.polymer.2017.12.005.  https://www.osti.gov/servlets/purl/1538758.

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@article{osti_1538758,

  title        = {Automatic, simultaneous control of polymer composition and molecular weight during free radical copolymer synthesis},

  author       = {McAfee, Terry and Montgomery, Rick D. and Zekoski, Thomas and Wu, Aide and Reed, Wayne F.},

  abstractNote = {Fully automatic, simultaneous control of polymer composition and molecular weight trajectories during free radical copolymer synthesis was achieved by coupling the continuous ACOMP data stream into a feedback controller which operated pumps for reactor feed of comonomers. The controller operates without recourse to a detailed kinetic model or reactivity ratios. Rather, it uses the fact that instantaneous copolymer chain composition is related to the instantaneous rate of consumption of comonomers, and the rate for each of these is described by rates α1 and α2 for comonomers 1 and 2, respectively. The instantaneous weight average molecular weight Mw,inst is proportional to total comonomer concentration via a constant p. Hence, target trajectories for composition and Mw can be independently prescribed and followed. Finally, since α1, α2 and p are directly measurable from the ACOMP data stream, their values can be constantly updated by the automatic controller during the reaction process to insure the target trajectories are followed.},

  doi          = {10.1016/j.polymer.2017.12.005},

  journal      = {Polymer},

  number       = C,

  volume       = 136,

  place        = {United States},

  year         = {Thu Dec 21 00:00:00 EST 2017},

  month        = {Thu Dec 21 00:00:00 EST 2017}

}

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Title: Automatic, simultaneous control of polymer composition and molecular weight during free radical copolymer synthesis

Abstract

Citation Formats

Model‐Based Production of Polymer Chains Having Precisely Designed End‐to‐End Gradient Copolymer Composition and Chain Topology Distributions in Controlled Radical Polymerization, A Review journal, May 2015

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A Systems Approach towards an Intelligent and Self‐Controlling Platform for Integrated Continuous Reaction Sequences journal, November 2014

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The Scattering of Light and the Radial Distribution Function of High Polymer Solutions journal, December 1948

Quantitative Contrasts in the Copolymerization of Acrylate- and Methacrylate-Based Comonomers journal, November 2006

Determination of Molecular Mass during Online Monitoring of Copolymerization Reactions journal, October 2007

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Electrostatically Enhanced Second and Third Virial Coefficients, Viscosity, and Interparticle Correlations for Linear Polyelectrolytes journal, May 2002

Dependence of polyelectrolyte apparent persistence lengths, viscosity, and diffusion on ionic strength and linear charge density journal, November 1991

Limiting Laws and Counterion Condensation in Polyelectrolyte Solutions II. Self‐Diffusion of the Small Ions journal, August 1969

Experimental Observation of Crossover from Noncondensed to Counterion Condensed Regimes during Free Radical Polyelectrolyte Copolymerization under High-Composition Drift Conditions journal, May 2009

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journal, May 2015

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journal, August 2006

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journal, January 2000

Estimation of copolymerization kinetic parameters by maximum likelihood method
journal, May 2004

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Penultimate unit effects in free radical copolymerization
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journal, September 2002

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journal, October 2013

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journal, December 1948

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journal, October 2007

Evolution of Composition, Molar Mass, and Conductivity during the Free Radical Copolymerization of Polyelectrolytes ^†
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Online Monitoring of Composition, Sequence Length, and Molecular Weight Distributions during Free Radical Copolymerization, and Subsequent Determination of Reactivity Ratios
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Automated batch characterization of polymer solutions by static light scattering and viscometry
journal, September 1999

Electrostatically Enhanced Second and Third Virial Coefficients, Viscosity, and Interparticle Correlations for Linear Polyelectrolytes
journal, May 2002

Dependence of polyelectrolyte apparent persistence lengths, viscosity, and diffusion on ionic strength and linear charge density
journal, November 1991

Limiting Laws and Counterion Condensation in Polyelectrolyte Solutions II. Self‐Diffusion of the Small Ions
journal, August 1969

Experimental Observation of Crossover from Noncondensed to Counterion Condensed Regimes during Free Radical Polyelectrolyte Copolymerization under High-Composition Drift Conditions
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Design and Control of Copolymer Composition Distribution in Living Radical Polymerization Using Semi‐Batch Feeding Policies: A Model Simulation
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