Real-time Fiber Optic Monitoring of Solution and Suspension Polymerization Processes

Puskás, Judit E.; Michel, Armin; Brister, LB; Tzaras, Eraclis; Marr, G.; Hoffman, Monika; Weiss, Karin

doi:10.1007/978-1-4615-0125-1_3

Cited by 5 publications

(2 citation statements)

References 23 publications

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“…Real‐time infrared (IR) spectroscopy is becoming increasingly popular with researchers to monitor polymerization and associated reactions 1–11. Similarly to traditional polymer science, most of the research focuses on homopolymerization, although reports on in situ Fourier transform infrared (FTIR) monitoring of copolymerization reactions have also appeared 8–13. Copolymers are immensely important; for instance only one‐third of the estimated 10 million metric tons of polystyrene produced commercially is used as a homopolymer; the balance is used in copolymers or blends 14.…”

Section: Introductionmentioning

confidence: 99%

A new high‐throughput approach to measure copolymerization reactivity ratios using real‐time FTIR monitoring

Shaikh

Puskás

Kaszás

2004

J. Polym. Sci. A Polym. Chem.

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This paper presents a novel high-throughput approach to measure copolymerization reactivity ratios from a single experiment using high-speed real-time Fourier transform infrared (FTIR) monitoring of the isobutylene/isoprene (IB/IP) system initiated by 2-chloro-2,4,4-trimethyl-pentane (TMPCl)/TiCl 4 in hexane/methyl chloride (Hx/MeCl) 60:40 v/v solvent at Ϫ80°C. Traditional polymer analysis is severely limited in this system, which is riddled by side reactions. The reactivity ratios calculated by linear (Mayo-Lewis and Kelen-Tü dös) methods and by a nonlinear least square (NLLS) method (van Herk algorithm) showed good agreement with r 1 ϭ1.32 and r 2 ϭ 0.74 calculated using Mayr's nucleophilicity scale. Combination of the Kelen-Tü dös and NLLS methods yielded r 1 ϭ 1.17 Ϯ 0.01 and r 2 ϭ 0.99 Ϯ 0.02. These values agree well with those reported by Thaler et al. but disagree with most reported data.

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Section: Introductionmentioning

confidence: 99%

A new high‐throughput approach to measure copolymerization reactivity ratios using real‐time FTIR monitoring

Shaikh

Puskás

Kaszás

2004

J. Polym. Sci. A Polym. Chem.

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“…Near IR monitoring has also been coupled to the ACOMP approach 50. A notable area for fruitful application of IR monitoring is in the field of polymerization in emulsions 51–53…”

Section: Measurement Of Monomer and Polymer Characteristics During Pomentioning

confidence: 99%

Fundamental Measurements in Online Polymerization Reaction Monitoring and Control with a Focus on ACOMP

Alb

Reed

2010

Macro Reaction Engineering

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Fundamental measurements in online polymerization reaction monitoring and control seek to avoid empirical and inferential models in data interpretation. One such approach making use of multiple detectors is automatic continuous online monitoring of polymerization reactions (ACOMP), wherein a continuous reactor stream is automatically, continuously diluted and conditioned to where measurements reflect intrinsic particle properties and not the interactions that can dominate measurements in concentrated media. Examples where dilute regime measurements are needed include static and dynamic light scattering, and reduced viscosity. This review focuses on ACOMP to illustrate a number of reaction contexts where fundamental measurements are used to gain a comprehensive picture of reaction characteristics.

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Kinetics and mechanisms in carbocationic polymerization: The quest for true rate constants

Puskás

Chan

McAuley

et al. 2005

J. Polym. Sci. A Polym. Chem.

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This article is a critical analysis of kinetic dataavailable on carbocationic polymerizations. A survey of published propagation rate constant (kp) data revealed several orders of magnitude differences. In this article, an explanation of this apparent discrepancy is offered with a case study involving the carbocationic polymerization of 2,4,6‐trimethylstyrene (TMS). With the polymerization mechanism originally proposed for this system, kp = 1.35 × 104 L mol−1 s−1 was extracted from experimental data with the Predici polyreaction package. The alternative mechanism yielded kp = 1.01 × 107 L mol−1 s−1, close to that predicted by Mayr's Linear Free Energy Relationship (LFER). We propose that true rate constants can only be obtained from direct competition experiments or from kinetic interpretation based on independently proven mechanisms. The second part of this review discusses critical analysis of the temperature and concentration dependence of various living IB systems. Comparison of the temperature dependence in systems initiated with 2‐ chloro‐2,4, 4‐ trimethylpentane (TMPCl)/TiCl4 from various laboratories yielded of ΔH ∼−25 and −34.5 kJ/mol for high and low TMPCl/TiCl4 ratios, respectively. Aromatic (cumyl‐type) initiators show ΔH ∼ −40 kJ/mol, whereas H2O/TiCl4 in the presence of the strong electron‐ pair donor dimethylacetamide gave ΔH = −12 kJ/mol. The significant differences indicate different underlying mechanisms with complex elementary reactions. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5394–5413, 2005

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Real-time Fiber Optic Monitoring of Solution and Suspension Polymerization Processes

Cited by 5 publications

References 23 publications

A new high‐throughput approach to measure copolymerization reactivity ratios using real‐time FTIR monitoring

A new high‐throughput approach to measure copolymerization reactivity ratios using real‐time FTIR monitoring

Fundamental Measurements in Online Polymerization Reaction Monitoring and Control with a Focus on ACOMP

Kinetics and mechanisms in carbocationic polymerization: The quest for true rate constants

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