Coupling of NMR to ACOMP for Terpolymerization Monitoring and Control

doi:10.1002/mren.201900039

The project goal was to create an energy saving paradigm shift in how polymers are manufactured in the 21st century. It used Automatic Continuous Online Monitoring of Polymerization reactions (ACOMP) integrated for the first time with automatic active control to create the innovative ‘ACOMP/Control Interface’, or ‘ACOMP/CI’. ACOMP/CI will begin the transformation from old, inefficient processes into highly evolved, energy and resource efficient ones. The ACOMP platform is broadly applicable to many types of reactions and processes throughout the vast polymer industry. The industry provides materials for sectors such as automotive, aerospace, oil recovery, agriculture, paints, resins, adhesives, pharmaceuticals andmore » therapeutic proteins, optics, electronics, lightweight building materials, and many more. The U.S. chemical industry is one of the last major sectors in which the U.S. has top global stature. It consumes 24% of all U.S. manufacturing energy, produces over $800B of product annually, supports 25% of the U.S. GDP and employs over 6 million people. It is also a major source of GHG emissions. Polymers make up approximately 30% of this sector. It is estimated that annually 60 TBtu of energy could be saved and 3 million tons less of GHG emissions produced by optimizing production in the polyolefin manufacturing sector alone. The project scope included first time design and prototyping of an ACOMP/CI, creation of active reaction controllers, and demonstration of control capabilities on ideal, low concentration polymerization reactions. All these elements of the scope were met, including advances and findings not originally anticipated. Extensions to more complex reactions, beyond the reactor capabilities of the current project ACOMP/CI, such as polyolefins and other high pressure/high temperature reactions, are being proposed in Fall 2017 to CESMII, a DoE based NNMI. The initial proposal was for a three year funded project, but this was reduced to a two year project and budget due to funding constraints. Hence, some of the original plans, such as adaptation of the ACOMP/CI to more relevant industrial processes, such as emulsion and dispersion technologies, could not be carried out. A third year of funding was requested at the end of the project, but DoE did not have resources to grant this. The sub-contractor Fluence Analytics (previously Advanced Polymer Monitoring Technologies, Inc) designed, prototyped, and commissioned a working ACOMP/CI by June 2015. The reaction characteristics to be automatically controlled were i) conversion kinetics, ii) molecular weight, iii) copolymer composition, and iv) simultaneous molecular weight and composition. A two pronged control strategy was used. The Tulane/Fluence group took a basic principles approach that did not rely on kinetic models. The LSU group took a more complex, non-linear model-oriented approach involving complete kinetic descriptions of the reaction system Each of these approaches proved successful in their own way. By April 2016 fully automatic control of conversion and weight average molecular weight, Mw, trajectories was achieved using the Tulane/Fluence (TF) basic principles controller. Similar results were obtained by the LSU non-linear model controller by August 2016. The demonstration system was aqueous free radical polymerization of acrylamide, Am. The control variables were temperature and semi-batch feed to the reactor of Am monomer and initiator. A demonstration of active manual conversion control in an industrial process using high solids in inverse emulsion polymerization of Am was achieved. During Summer 2016 the TF controller was used in conjunction with a chain transfer agent, another control variable, to automatically produce multi-modal molecular weight distributions, MWD, in a single reactor. Industrially, multi-modal MWD are produced by mixing products made in separate reactors, requiring significant extra time, energy, and reactor resources. Recognizing the industrial potential a patent on automatic production of multi-modal polymers was filed, and DoE acknowledged. In Fall 2016 the TF team developed a basic principles controller for copolymer composition and demonstrated it on aqueous free radical copolymerization of comonomers Am and styrene sulfonate, SS. TF then fused the Mw and composition controllers to achieve simultaneous control of both Mw and copolymer composition trajectories. Numerous simultaneous trajectories were demonstrated, including a trimodal composition distribution with constant Mw. Meanwhile, the LSU group developed a Kalman filter to improve the results of their automatic Mw and conversion controller and successful tests were made. During the project the TF team developed a means of computing full MWD during polymer synthesis without need for any chromatographic separation, based on model distributions. This means the polymer product is ‘born characterized’ and this can eliminate post-manufacture analytical laboratory quality control. TF filed a joint patent application on this new approach to chromatography-free determination of MWD with acknowledgment to DoE. The Tulane group obtained a 60MHz NMR during the project and recently completed the first work on separating three comonomers, Am, SS, and Na-acrylate, with a first demonstration of terpolymer composition control with the TF basic principles controller. Widespread dissemination of ACOMP/CI in the polymer manufacturing sector will bolster DoE goals of energy efficiency and reduced GHG emissions: The ability to monitor and actively control polymerization reactions will lead to more efficient use of energy and non-renewable resources, plant and labor time, increase the safety of manufacturing personnel, and will enhance product quality and lead to feasibility of manufacturing of polymers currently too complex for industrial scale production, while leading to less GHG emissions per kilo of product, and allowing for increased U.S. competitiveness in this enormous manufacturing sector. When ACOMP/CI is expanded to the polyolefin industry it is estimated that 60 TeraBTU/year of energy can be saved. Much of this saving is anticipated to come from optimized control of grade changeovers in steady state reactors and maintenance of steady states. Conclusions: ACOMP’s ability to provide continuous realtime data streams of measured polymer and reaction characteristics made it possible, for the first time, to directly and automatically control free radical polymerization reactions. An industrial client of Fluence Analytics has requisitioned the first ACOMP/CI which uses the TF basic principles controller. This sets the stage for FA to add control features to the ACOMP systems it has begun to install on the industrial scale beginning in 2014. Recommendations: This successful project was mainly limited to ideal polymerizations not of an industrial sort. The most energy intensive portion of polymer manufacturing is polyolefins. Adoption of ACOMP/CI to this enormous industrial sector faces the enormous challenges of high temperature, high pressure continuous sampling and high temperature sensor operation to obtain the continuous data needed for direct reaction control. The project team has a strategy for achieving this ambitious goal and will present it in Fall 2017 as a proposal to CESMII/DoE. It is recommended that this upcoming proposal be funded in order to make full use of the achievements of this just ended DoE project as the next step towards making polyolefin ACOMP/CI an energy saving reality. It is projected that ACOMP/CI can have its first polyolefin testbed demonstrations within two years of beginning the proposed project.

Title: Coupling of NMR to ACOMP for Terpolymerization Monitoring and Control

Citation Formats

Inferential Conversion and Composition Monitoring via Microcalorimetric Measurements in Emulsion Terpolymerization
journal, December 2007

Automatic Control of Polymer Molecular Weight during Synthesis
journal, September 2016

Polymer Composition Control in Emulsion Co- and Terpolymerizations
journal, March 2002

Online model-based control of an emulsion terpolymerisation process
journal, May 2009

Macromol. Chem. Phys. 1/2018
journal, January 2018

Mathematical modeling of diffusion-controlled free-radical terpolymerization reactions
journal, January 2003

Terpolymerization monitoring with ATR-FTIR spectroscopy: Terpolymerization Monitoring
journal, April 2001

Online Optimal Feedback Control of Polymerization Reactors: Application to Polymerization of Acrylamide–Water–Potassium Persulfate (KPS) System
journal, June 2017

Thermoresponsive gels based on ABC triblock copolymers: effect of the length of the PEG side group
journal, January 2016

High solids content emulsion terpolymerization of vinyl acetate, methyl methacrylate and butyl acrylate. II. Open loop composition control
journal, July 1994

Synthesis of new D-A1–D-A2 type low bandgap terpolymers based on different thiadiazoloquinoxaline acceptor units for efficient polymer solar cells
journal, January 2016

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

Automatic, simultaneous control of polymer composition and molecular weight during free radical copolymer synthesis
journal, January 2018

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

Poly(N-vinyl-2-pyrrolidone-maleic anhydride-styrene) grafted terpolymer: Synthesis, characterization, and bactericidal property evaluation against E. coli and S. epidermidis
journal, July 2017

Evolution of Composition, Molar Mass, and Conductivity during the Free Radical Copolymerization of Polyelectrolytes ^†
journal, July 2007

Light-Scattering Studies of Copolymers: i. Effect of Heterogeneity of Chain Composition on the Molecular Weight
journal, December 1958

Synthesis and photovoltaic properties of three different types of terpolymers
journal, January 2017

On-Line Monitoring of Emulsion Terpolymerization Processes
journal, November 2001

Synthesis and characterization of SSS/HAM/AA terpolymer as a fluid loss additive for oil well cement: Research Article
journal, February 2018

Batch separation studies for the removal of heavy metal ions using a chelating terpolymer: Synthesis, characterization and isotherm models
journal, September 2013

Multicompartment Nanoparticles of Poly(4-vinylpyridine) Graft Block Terpolymer: Synthesis and Application as Scaffold for Efficient Au Nanocatalyst
journal, February 2015

Infrared process monitoring of conjugated linoleic acid/styrene/butyl acrylate bulk and emulsion terpolymerization
journal, March 2016

Emulsion co- and terpolymerization of styrene, methyl methacrylate and methyl acrylate. II. Control of emulsion terpolymer microstructure with optimal addition profiles
journal, April 1996

Copolymers in dilute solution. I. Preliminary results for styrene-methyl methacrylate
journal, April 1955

Title: Coupling of NMR to ACOMP for Terpolymerization Monitoring and Control

Citation Formats

Inferential Conversion and Composition Monitoring via Microcalorimetric Measurements in Emulsion Terpolymerization journal, December 2007

Automatic Control of Polymer Molecular Weight during Synthesis journal, September 2016

Polymer Composition Control in Emulsion Co- and Terpolymerizations journal, March 2002

Online model-based control of an emulsion terpolymerisation process journal, May 2009

Macromol. Chem. Phys. 1/2018 journal, January 2018

Mathematical modeling of diffusion-controlled free-radical terpolymerization reactions journal, January 2003

Terpolymerization monitoring with ATR-FTIR spectroscopy: Terpolymerization Monitoring journal, April 2001

Online Optimal Feedback Control of Polymerization Reactors: Application to Polymerization of Acrylamide–Water–Potassium Persulfate (KPS) System journal, June 2017

Thermoresponsive gels based on ABC triblock copolymers: effect of the length of the PEG side group journal, January 2016

High solids content emulsion terpolymerization of vinyl acetate, methyl methacrylate and butyl acrylate. II. Open loop composition control journal, July 1994

Synthesis of new D-A1–D-A2 type low bandgap terpolymers based on different thiadiazoloquinoxaline acceptor units for efficient polymer solar cells journal, January 2016

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

Automatic, simultaneous control of polymer composition and molecular weight during free radical copolymer synthesis journal, January 2018

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

Poly(N-vinyl-2-pyrrolidone-maleic anhydride-styrene) grafted terpolymer: Synthesis, characterization, and bactericidal property evaluation against E. coli and S. epidermidis journal, July 2017

Evolution of Composition, Molar Mass, and Conductivity during the Free Radical Copolymerization of Polyelectrolytes † journal, July 2007

Light-Scattering Studies of Copolymers: i. Effect of Heterogeneity of Chain Composition on the Molecular Weight journal, December 1958

Synthesis and photovoltaic properties of three different types of terpolymers journal, January 2017

On-Line Monitoring of Emulsion Terpolymerization Processes journal, November 2001

Synthesis and characterization of SSS/HAM/AA terpolymer as a fluid loss additive for oil well cement: Research Article journal, February 2018

Batch separation studies for the removal of heavy metal ions using a chelating terpolymer: Synthesis, characterization and isotherm models journal, September 2013

Multicompartment Nanoparticles of Poly(4-vinylpyridine) Graft Block Terpolymer: Synthesis and Application as Scaffold for Efficient Au Nanocatalyst journal, February 2015

Infrared process monitoring of conjugated linoleic acid/styrene/butyl acrylate bulk and emulsion terpolymerization journal, March 2016

Emulsion co- and terpolymerization of styrene, methyl methacrylate and methyl acrylate. II. Control of emulsion terpolymer microstructure with optimal addition profiles journal, April 1996

Copolymers in dilute solution. I. Preliminary results for styrene-methyl methacrylate journal, April 1955