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Monitoring of Vinyl Acetate–Ethylene Processes: An Industrial Perspective

  • Eric Frauendorfer
  • Muhammad Babar
  • Timo Melchin
  • Wolf-Dieter Hergeth
Chapter
Part of the Advances in Polymer Science book series (POLYMER, volume 281)

Abstract

Monitoring of vinyl acetate–ethylene (VAE) processes plays a crucial role in achieving high process efficiency in industry while ensuring process safety and the needed product quality. Different methods are applied along the process chain, which includes production of the VAE polymer dispersion in high pressure reactors, degassing of the product back to atmospheric pressure, storage and shipping, and spray drying of the polymer to create a dispersible polymer powder. Properties of interest to monitor on a routine basis can be process related, such as heat output and conversion, or product related, such as total solids, viscosity, pH, particle size distribution, moisture content, and chemical composition. Other techniques can also be used to gain further knowledge of the process (e.g., mixing behavior) and of the product (e.g., polymer structure, volatile organic compounds, and biostability). Different monitoring techniques are discussed, focusing on their applicability in the industrial process under consideration.

Keywords

Online analytics Polymerization Process monitoring Vinyl acetate-ethylene copolymer 

References

  1. 1.
    Gy P (2004) Part IV: 50 years of sampling theory – a personal history. Chemom Intell Lab Syst 74:49–60Google Scholar
  2. 2.
    Petersen L, Minkkinen P, Esbensen KH (2005) Representative sampling for reliable data analysis, theory of sampling. Chemom Intell Lab Syst 77:261–277Google Scholar
  3. 3.
    Smith PL (2008) An introduction to general sampling: reducing bias and variation in bulk sampling. J GXP Compliance 12(4):60–65Google Scholar
  4. 4.
    Smith PL (2008) Error and variation in bulk material sampling. J GXP Compliance 12(5):69–76Google Scholar
  5. 5.
    Smith PL (2009) Q & A on sampling bulk materials. J GXP Compliance 13(1):67–73Google Scholar
  6. 6.
    Allen T (2003) Powder sampling and particle size determination. Elsevier, LondonGoogle Scholar
  7. 7.
    Muzzio FJ, Goodridge CL, Alexander A, Arratia P, Yang H, Sudah O, Mergen G (2002) Sampling and characterization of pharmaceutical powders and granular blends. Int J Pharm 250(1):51–64Google Scholar
  8. 8.
    Muzzio FJ, Robinson P, Wightman C, Brone D (1997) Sample practices in powder blending. Int J Pharm 155(2):153–178Google Scholar
  9. 9.
    Chrysler, Ford, General Motors (2010) Measurement system analysis4th edn. Automotive Industry Action Group, SouthfieldGoogle Scholar
  10. 10.
    Apley QJ , Cliff WC, Creer JM (1984) Sampling device for withdrawing a representative sample from single and multi-phase flows. Patent US 4,442,720 AGoogle Scholar
  11. 11.
    Enohnyaket P, Kreft T, Alb AM, Drenski MF, Reed WF (2007) Determination of molecular mass during online monitoring of copolymerization reactions. Macromolecules 40:8040Google Scholar
  12. 12.
    Alb AM, Paril A, Çatalgil-Giz H, Giz A, Reed WF (2007) Evolution of composition, molar mass, and conductivity during the free radical copolymerization of polyelectrolytes. J Phys Chem B 111:8560PubMedGoogle Scholar
  13. 13.
    Alb AM, Reed WF (2008) Simultaneous monitoring of polymer and particle characteristics during emulsion polymerization. Macromolecules 41:2406–2414Google Scholar
  14. 14.
    Alb AM, Reed WF (2009) Online monitoring of molecular weight and other characteristics during semibatch emulsion polymerization under monomer starved and flooded conditions. Macromolecules 42:8093–8101Google Scholar
  15. 15.
    Kreft T, Reed WF (2009) Predictive control of average compositionand molecular weight distributions in semibatch free radical copolymerization reactions. Macromolecules 42(15):5558–5565Google Scholar
  16. 16.
    Reed WF, Alb AM (eds) (2013) Monitoring polymerization reactions: from fundamentals to applications. Wiley, HobokenGoogle Scholar
  17. 17.
    Moritz H-U (1989) Polymerizaiton calorimetry – a powerful tool for reactor control. In: Reichert KH, Geisler W (eds) Polymer reaction engineering. VCH, Weinheim, pp 248–266Google Scholar
  18. 18.
    Fonseca GE, Dubé MA, Penlidis A (2009). Macromol React Eng 3:327Google Scholar
  19. 19.
    Landau RN (1996) Expanding the role of reaction calorimetry. Thermochim Acta 289(2):101–126Google Scholar
  20. 20.
    Gesthuisen R, Krämer S, Niggemann G, Leiza JR, Asua JM (2005) Determining the best reaction calorimetry technique: theoretical development. Comput Chem Eng 29:349–365Google Scholar
  21. 21.
    Esposito M, Sayer C, de Araújo PHH (2010) In-line monitoring of emulsion polymerization reactions combining heat flow and heat balance calorimetry. Macromol React Eng 4:682–690Google Scholar
  22. 22.
    Tietze A, Ludtke I, Reichert K-H (1996) Temperature oscillation calorimetry in stirred tank reactors. Chem Eng Sci 51:3131–3137Google Scholar
  23. 23.
    Hergeth WD, Jaeckle C, Krell M (2003) Industrial process monitoring of polymerization and spray drying processes. Polym React Eng 11:663Google Scholar
  24. 24.
    Elizalde O, Azpeitia M, Reis MM, Asua LM, Leiza JR (2005) Monitoring emulsion polymerization reactors: calorimetry versus Raman spectroscopy. Ind Eng Chem Res 44:7200–7207Google Scholar
  25. 25.
    Elizalde O, Leiza JR, Asua JM (2004). Macromol Symp 206:135–148Google Scholar
  26. 26.
    Lamb DJ, Fellows CM, Morrison BR, Gilbert RG (2005) A critical evaluation of reaction calorimetry for the study of emulsion polymerization systems: thermodynamic and kinetic aspects. Polymer 46:285–294Google Scholar
  27. 27.
    Frauendorfer E, Wolf A, Hergeth W-D (2010) Polymerization online monitoring. Chem Eng Technol 33:1767–1778Google Scholar
  28. 28.
    BenAmor S, Colombié D, McKenna T (2002) Online reaction calorimetry. Applications to the monitoring of emulsion polymerization without samples or models of the heat-transfer coefficient. Ind Eng Chem Res 41:4233–4241Google Scholar
  29. 29.
    Hergeth W-D (2011) On-line monitoring of chemical reactions. Ullmann’s encyclopedia of industrial chemistry7th edn. Wiley-VCH, Weinheim, pp 345–398Google Scholar
  30. 30.
    Kessler RW, Kessler W, Zikulnig-Rusch E (2016) A critical summary of spectroscopic techniques and their robustness in industrial PAT applications. Chem Ing Tech 88:710–721Google Scholar
  31. 31.
    Chatzi EG, Kammona O, Kiparissides C (1997) Use of a midrange infrared optical-fiber probe for the on-line monitoring of 2-ethylhexyl acrylate/styrene emulsion copolymerization. J Appl Polym Sci 63:799–809Google Scholar
  32. 32.
    Hua H, Dube MA (2001) Terpolymerization monitoring with ATR-FTIR spectroscopy. J Polym Sci Part A Polym Chem 39:1860–1876Google Scholar
  33. 33.
    Roberge S, Dube MA (2007) Inline monitoring of styrene/butyl acrylate miniemulsion polymerization with attenuated total reflectance/Fourier transform infrared spectroscopy. J Appl Polym Sci 103:46–52Google Scholar
  34. 34.
    Schuchardt P, Siesler HW (2017) Real-time analysis of the polymerization kinetics of 1,4-butanediol and 4,4′-diphenylmethanediisocyanate by fiber-coupled Fourier transform infrared spectroscopy. Anal Bioanal Chem 409:833–839PubMedGoogle Scholar
  35. 35.
    Mettler-Toledo (2017) FTIR spectroscopy with in situ reaction monitoring. Mettler-Toledo, Columbia. http://www.mt.com/us/en/home/products/L1_AutochemProducts/ReactIR.html. Accessed 17 Feb 2017
  36. 36.
    Santos AF, Silva FM, Lenzi MK, Pinto JC (2005) Monitoring and control of polymerization reactors using NIR spectroscopy. Polym-Plast Technol Eng 44:1–61Google Scholar
  37. 37.
    Cherfi A, Fevotte G, Novat C (2002) Robust on-line measurement of conversion and molecular weight using NIR spectroscopy during solution polymerization. J Appl Polym Sci 85:2510–2520Google Scholar
  38. 38.
    Sheibat-Othman N, Fevotte G, Peycelon D, Egraz J-B, Asua J-M (2004) Control of polymer molecular weight using near infrared spectroscopy. AICHE J 50:654Google Scholar
  39. 39.
    Reis MM, Araujo PHH, Sayer C, Guidici R (2003) Correlation between polymer particle size and in-situ NIR spectra. Macromol Rapid Commun 24:620–624Google Scholar
  40. 40.
    Reis MM, Araujo PHH, Sayer C, Guidici R (2004) In situ near-infrared spectroscopy for simultaneous monitoring of multiple process variables in emulsion copolymerization. Ind Eng Chem Res 43:7243–7250Google Scholar
  41. 41.
    Frauendorfer E, Hergeth W-D (2016) Prozessanalytik bei der zerstäubungstrocknung – beispiele und herausforderungen. Chem Ing Tech 88:777–785Google Scholar
  42. 42.
    Schrader B (1995) Infrared and Raman spectroscopy: methods and applications. VCH, WeinheimGoogle Scholar
  43. 43.
    Elizalde O, Leiza JR (2009) Raman application in emulsion polymerization systems. In: Amer MS (ed) Raman spectroscopy for soft matter applications. Wiley-Blackwell, New York, pp 95–144Google Scholar
  44. 44.
    Frauendorfer E, Hergeth W-D (2017) Industrial application of Raman spectroscopy for control and optimization of vinyl acetate resin polymerization. Anal Bioanal Chem 409:631–636PubMedGoogle Scholar
  45. 45.
    Reis MM, Araujo PHH, Sayer C, Guidici R (2003) Evidences of correlation between polymer particle size and Raman scattering. Polymer 44:6123–6128Google Scholar
  46. 46.
    Hergeth W-D, Codella PJ (1994) Monomers in polymer dispersions. Part IV: partition of acrylonitrile in rubber latex as studied by Raman spectroscopy. Appl Spectrosc 48:900–903Google Scholar
  47. 47.
    Anton F, Lindemann C, Hitzmann B, Reardon KF, Scheper T (2010) Fluorescence sensors for bioprocess monitoring. In: Flickinger MC (ed) Encyclopedia of industrial biotechnology: bioprocess, bioseparation, and cell technology. Wiley, New York, pp 2482–2491Google Scholar
  48. 48.
    Hass R, Reich O (2011) Photon density wave spectroscopy for dilution-free sizing of highly concentrated nanoparticles during starved-feed polymerization. Chem Phys Chem 12:2572–2575PubMedGoogle Scholar
  49. 49.
    Hass R, Munzke D, Reich O (2010) Inline-partikelgrößenmesstechniken für suspensionen und emulsionen. Chem Ing Tech 82:477–490Google Scholar
  50. 50.
    Maret G (1997) Diffusing-wave spectroscopy. Curr Opin Colloid Interface Sci 2:251–257Google Scholar
  51. 51.
    Singha N (2001) Use of fiber optics quasi-elastsic light scattering (FOQELS) in the particle sizing of polymer lattices. Kaut Gummi Kunstst 54(3):97–100Google Scholar
  52. 52.
    Hauptmann P, Dinger F, Säuberlich R (1985) A sensitive method for polymerization control based on ultrasonic measurements. Polymer 26:1741–1744Google Scholar
  53. 53.
    Hergeth W-D, Starre P, Schmutzler K, Wartewig S (1988) Polymerizations in the presence of seeds: 3. Emulsion polymerization of vinyl acetate in the presence of quartz powder. Polymer 29:1323–1328Google Scholar
  54. 54.
    Chai X-S, Hou QX, Schork FJ (2004) Determination of residual monomer in polymer latex by full evaporation headspace gas chromatography. J Chromatogr A 1040(2):163–167PubMedGoogle Scholar
  55. 55.
    Leiza JR, de la Cal JC, Montes M, Asua JM (1993) Online monitoring of conversion and polymer composition in emulsion polymerization systems. Process Control Qual 4(3):197–210Google Scholar
  56. 56.
    Noel LFJ, Brouwer ECP, van Herk AM, German AL (1995) On-line gas chromatography and densimetry to obtain partial conversions of both monomers in emulsion copolymerization. J Appl Polym Sci 57:245Google Scholar
  57. 57.
    Zhou M, Lee J, Zhu H, Nidetz R, Kurabayashi K, Fan X (2016) A fully automated portable gas chromatography system for sensitive and rapid quantification of volatile organic compounds in water. RSC Adv 6:49416–49424Google Scholar
  58. 58.
    McAfee T, Leonardi N, Montgomery R, Siqueira J, Zekoski T, Drenski MF, Reed WF (2016) Automatic control of polymer molecular weight during synthesis. Macromolecules 49:7170–7183Google Scholar
  59. 59.
    Reed WF, Drenski MF, From PCT Int. Appl (2016) Systems and methods for control of polymer reactions and processing using automatic continuous online monitoring. Patent WO 2016054138 A1 20160407Google Scholar
  60. 60.
    Reed WF, From PCT Int. Appl (2016) Device and method for changing solution conditions in serial flow. Patent WO 2016061024 A2 20160421Google Scholar
  61. 61.
    Reed WF, Drenski MF, From PCT Int. Appl (2016) Systems and methods for predicting and controlling the properties of a chemical species during a time-dependent process. Patent WO 2016118507 A1 20160728Google Scholar
  62. 62.
    Reed WF, From PCT Int. Appl (2017) Scheduling analysis and throughput of macromolecular solutions based on light scattering measurements. Patent WO 2017015499 A1 20170126Google Scholar
  63. 63.
    Rosenfeld C, Serra C, O’Donohue S, Hadziioannou G (2007) Continuous online rapid size exclusion chromatography monitoring of polymerizations – CORSEMP. Macromol React Eng 1:547–552Google Scholar
  64. 64.
    Maka AC, Williams RP, Pasch H (2016) Field flow fractionation for the size, molar mass, and gel content analysis of emulsion polymers for water-based coatings. Macromol Chem Phys 217:2027–2040Google Scholar
  65. 65.
    Sweetman SJ, Immanuel CD, Malik TI, Emmett S, Williams N (2008) Simultaneous controllability of PSD and MWD in emulsion polymerisation. Macromol React Eng 2:382–397Google Scholar
  66. 66.
    Colnago LA (2014) Why is inline NMR rarely used as industrial sensor? Challenges and opportunities. Chem Eng Technol 37(2):191–203Google Scholar
  67. 67.
    Ibbett RN (ed) (1993) NMR spectroscopy of polymers. Blackwell Academic & Professional, GlasgowGoogle Scholar
  68. 68.
    Hofmann M, Herrmann A, Ok S, Franz C, Kruk D, Saalwächter K, et al. (2011) Polymer dynamics of polybutadiene in nanoscopic confinement as revealed by field cycling 1H NMR. Macromolecules 44:4017–4021Google Scholar
  69. 69.
    Mujtaba A, Keller M, Ilisch S, Radusch HJ, Thurn-Albrecht T, Saalwächter K, et al. (2012) Mechanical properties and cross-link density of styrene–butadiene model composites containing fillers with bimodal particle size distribution. Macromolecules 45:6504–6515Google Scholar
  70. 70.
    Räntzsch V, Wilhelm M, Guthausen G (2016) Hyphenated low-field NMR techniques: combining NMR with NIR, GPC/SEC and rheometry. Magn Reson Chem 54:494–501PubMedGoogle Scholar
  71. 71.
    Dalitz F, Cudaj M, Maiwald M, Guthausen G (2012) Process and reaction monitoring by low-field NMR spectroscopy. Prog Nucl Magn Reson Spectrosc 60:52–70PubMedGoogle Scholar
  72. 72.
    Singh K, Blümich B (2016) NMR spectroscopy with compact instruments. Trends Anal Chem 83:12–26Google Scholar
  73. 73.
    Cudaj M, Guthausen G, Hofe T, Wilhelm M (2011) SEC-MR-NMR: online coupling of size exclusion chromatography and medium resolution NMR spectroscopy. Macromol Rapid Commun 32:665–670PubMedGoogle Scholar
  74. 74.
    Cudaj M, Guthausen G, Hofe T, Wilhelm M (2012) Online coupling of size-exclusion chromatography and low-field 1H NMR spectroscopy. Macromol Chem Phys 213:1933–1943Google Scholar
  75. 75.
    Harbou EV, Behrens R, Berje J, Brächer A, Hasse H (2016) Studying fast reaction kinetics with online NMR spectroscopy. Chem Ing Tech 89:369–378. doi: 10.1002/cite.201600068CrossRefGoogle Scholar
  76. 76.
    Duewel M, Vogel N, Weiss CK, Landfester K, Spiess HW, Münnemann K (2012) Online monitoring of styrene polymerization in miniemulsion by hyperpolarized 129xenon NMR spectroscopy. Macromolecules 45:1839–1846Google Scholar
  77. 77.
    Sans V, Porwol L, Dragone V, Cronin L (2015) A self optimizing synthetic organic reactor system using real-time in-line NMR spectroscopy. Chem Sci 6:1258–1264PubMedGoogle Scholar
  78. 78.
    Vargas MA (2010) online low-field 1H NMR spectroscopy: monitoring of emulsion polymerization of butyl acrylate. Macromolecules 43:5561–5568Google Scholar
  79. 79.
    Landfester K, Spiegel S, Born R, et al. (1998) On-line detection of emulsion polymerization by solid-state NMR spectroscopy. Colloid Polym Sci 276:356Google Scholar
  80. 80.
    Landfester K, Spiess HW (1998) Characterization of interphases in core – shell latexes by solid-state NMR. Acta Polym 49:451–464Google Scholar
  81. 81.
    Adams A (2016) Analysis of solid technical polymers by compact NMR. Trends Anal Chem 83:107–119Google Scholar
  82. 82.
    Meyer K, Kern S, Zientek N, Guthausen G, Maiwald M (2016) Process control with compact NMR. Trends Anal Chem 83:39–52Google Scholar
  83. 83.
    Foley DA, Bez E, Codina A, Colson KL, Fey M, Krull R, et al. (2014) NMR flow tube for online NMR reaction monitoring. Anal Chem 86:12008–12013PubMedGoogle Scholar
  84. 84.
    Santos AF, Lima AL, Pinto JC, Graillat C, McKenna TF (2003) Online monitoring of the evolution of the number of particles in emulsion polymerization by conductivity measurements. I. Model formulation A. J Appl Polym Sci 90(5):1213–1226Google Scholar
  85. 85.
    Farshchi F, Santos AF, Othman S, Hammouri H, McKenna TF (2004) Monitoring of emulsion polymerization using conductimetry coupled with calorimetry. In: 8th international workshop on polymer reaction engineering, Hamburg, 3–6 October 2004Google Scholar
  86. 86.
    Santos AF, Lima EL, Pinto JC, Graillat C, McKenna TF (2004) On-line monitoring of the evolution of number of particles in emulsion polymerization by conductivity measurements. II. Model validation. J Appl Polym Sci 91(2):941–952Google Scholar
  87. 87.
    Graillat C, Santos A, Pinto JC, McKenna TF (2004) On-line monitoring of emulsion polymerisation using conductivity measurements. Macromol Symp 206:433–442Google Scholar
  88. 88.
    Zhao F (2011) Online conductivity and stability in emulsion polymerization of n-butyl methacrylate. Theses and Dissertations. Paper 1276, Lehigh University, BethlehemGoogle Scholar
  89. 89.
    Ye Z, Yang CL, Ma L, Wei HY, Banasiak R, Soleimani M (2013) Volumetric soft field and hard field tomography: MIT, ECT, EIR, cone beam CT. In: 7th World Congress on Industrial Process TomographyGoogle Scholar
  90. 90.
    Sharifi M, Young B (2013) Electrical resistance tomography (ERT) applications to chemical engineering. Chem Eng Res Des 91(9):1625–1645Google Scholar
  91. 91.
    Fransolet E, Crine M, L’Homme G, Toye D, Marchot P (2002) Electrical resistance tomography sensor simulations: comparison with experiments. Meas Sci Technol 13:1239–1247Google Scholar
  92. 92.
    McClements DJ, Fairley P (1991) Ultrasonic pulse echo reflectometer. Ultrasonics 29(1):58–62Google Scholar
  93. 93.
    Jaworski A, Dyakowski T (2001) Application of electrical capacitance tomography for measurement of gas-solids flow characteristics in a pneumatic conveying system. Meas Sci Technol 12:1605–1616Google Scholar
  94. 94.
    Runt JS, Fitzgerald JJ (eds) (1997) Dielectric spectroscopy of polymeric materials. Fundamentals and applications. American Chemical Society, WashingtonGoogle Scholar
  95. 95.
    Scrosati B (ed) (1993) Applications of electroactive polymers. Chapman and Hall, LondonGoogle Scholar
  96. 96.
    Gray FM (1991) Solid polymer electrolytes – fundamentals and technological applications. VCH, New YorkGoogle Scholar
  97. 97.
    Zardalidis G, Floudas G (2012) Pressure effects on the dynamic heterogeneity of miscible poly(vinyl acetate)/poly(ethylene oxide) blends. Macromolecules 45:6272–6280Google Scholar
  98. 98.
    Madouly SA, Mansoour AA, Abdou NY (2007) Molecular dynamics of amorphous/crystalline polymer blends studied by broadband dielectric spectroscopy. Eur Polym J 43:1892–1904Google Scholar
  99. 99.
    Füllbrandt M, Purohit PJ, Schönhals A (2013) Combined FTIR and dielectric investigation of poly(vinyl acetate) adsorbed on silica particles. Macromolecules 46(11):4526–4632Google Scholar
  100. 100.
    Jensen JN, Johnson JD (1989) Specificity of the DPD and amperometric titration methods for free available chlorine: a review. J Am Water Works Assoc 81(12):59–64Google Scholar
  101. 101.
    Rice EW, Baird R, Eaton AD (eds) (1992) Standard methods for the examination of water and wastewater. American Public Health Association, WashingtonGoogle Scholar
  102. 102.
    Udenfriend S (ed) (1969) Florescence assay in biology and medicine. Academic, LondonGoogle Scholar

Copyright information

© Springer International Publishing AG 2017

Authors and Affiliations

  • Eric Frauendorfer
    • 1
  • Muhammad Babar
    • 1
  • Timo Melchin
    • 1
  • Wolf-Dieter Hergeth
    • 1
  1. 1.R&D DepartmentWacker Chemie AGBurghausenGermany

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