Real-Time Monitoring of the Stable Free Radical Polymerization of Styrene via in-Situ Mid-Infrared Spectroscopy

Pasquale, Anthony J.; Long, Timothy Edward

doi:10.1021/ma9912498

Cited by 45 publications

(46 citation statements)

References 20 publications

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“…The FTIR spectra were collected every minute and the change of absorbance at 938 cm 21 [@CH 2 wags of the DEA and PEGMA (M n 5 475)] was used to provide the conversion of monomers during the polymerization. 27,28 DEA (4.8 g) was introduced by syringe until the absorbance of 938 cm 21 kept almost constant and then the second monomer PEGMA (M n 5 475, 6.4 g) was introduced to continue the polymerization. A tiny amount of CuBr 2 catalyst (0.0143 g, 0.064 mmol) and ligand HMTETA (0.164 mL, 0.64 mmol) were used together with a sufficiently large excess of reducing agent Sn(Oct) 2 (0.259 g, 0.64 mmol).…”

Section: Experimental Section Materialsmentioning

confidence: 99%

Structure–property relationship of pH‐sensitive (PCL)₂(PDEA‐b‐PPEGMA)₂ micelles: Experiment and DPD simulation

et al. 2014

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The experiment and dissipative particle dynamics simulation were carried out on four polymers with different block ratios for the investigation of the structure-property relationship of (poly(e-caprolactone) 2 -[poly(2-(diethylamino)ethyl methacrylate)-b-poly(poly(ethylene glycol) methyl ether methacrylate)] 2 [(PCL) 2 (PDEA-b-PPEGMA) 2 ] micelles. The miktoarm star polymers assembled into spherical micelles composed of PCL core, pH-sensitive PDEA mesosphere and poly (ethylene glycol) methyl ether methacrylate (PPEGMA) shell. When decreasing pH from 7.4 to 5.0, the hydrodynamic diameter and transmittance of (PCL) 2 (PDEA-b-PPEGMA) 2 micelles increased along with globule-unevenextended conformational transitions, owing to the protonation of tertiary amine groups of DEA at lower pH conditions. Doxorubicin (DOX) was mainly loaded in the pH-sensitive layer, and more DOX were loaded in the core when increasing drug concentrations. The in vitro DOX release from the micelles was significantly accelerated by decreasing pH from 7.4 to 5.0. The results demonstrated that the pH-sensitive micelles could be used as an efficient carrier for hydrophobic anticancer drugs, achieving controlled and sustained drug release.

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Section: Experimental Section Materialsmentioning

confidence: 99%

Structure–property relationship of pH‐sensitive (PCL)₂(PDEA‐b‐PPEGMA)₂ micelles: Experiment and DPD simulation

et al. 2014

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“…[4] The in-line ATR-FTIR investigations of the carbonylation of epoxides and a mechanistic understanding of these processes were demonstrated by Allmendinger et al [5] Lizotte, Long and Pasquale et al presented the real-time monitoring of the radical polymerizations of acrylate systems and styrene and also the synthesis of maleic anhydride-cyclic olefin alternating copolymers. [6,11,12] Moreover, they calculated the monomer conversions and determined the kinetic data.…”

Section: Full Papermentioning

confidence: 99%

“…That's why the original second-order kinetic law is reduced to the pseudofirst-order kinetic law (1). [3,6,[10][11][12] À d½Conc dt ¼ k app ½Conc…”

Section: Ir Monitoringmentioning

confidence: 99%

Kinetic Studies of Metallocene‐Catalyzed Copolymerization of Propene with 10‐Undecene‐1‐ol Using In‐Line FTIR Spectroscopy

Sahre

Schulze

Eichhorn

et al. 2007

Macro Chemistry & Physics

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The present study describes the quantitative monitoring of the metallocene‐catalyzed copolymerization of propene with 10‐undecene‐1‐ol (UO) by in‐line ATR‐FTIR spectroscopy in order to obtain kinetic data. For the description of the time dependency of this copolymerization reaction a pseudo‐first‐order rate law was used. The apparent rate constant kapp of the comonomer consumption could be determined by evaluation of the integral absorbances of characteristic IR bands of the double bond of UO and of special IR determined concentration profiles of that comonomer using chemometric tools. The apparent rate constants determined by the integral absorbances of the ν CC band (stretching vibrations) range of 0.32–0.66 × 10−4 s−1 whereas evaluation of the absolute concentrations of the comonomer yields rate constants of 0.29–0.57 × 10−4 s−1. Variations within the rate constants obtained from different experimental runs point to a certain complexity of the reaction and a significant dependence of the copolymerization on the exact polymerization procedure.magnified image

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“…In situ FTIR monitoring was performed with an ASI Applied Systems ReactIR TM 1000 reaction analysis system with a stainless steel DiComp TM probe. [34,35] A comparison of peak height versus a common baseline point was performed to eliminate data scatter due to baseline drift.…”

Section: Methodsmentioning

confidence: 99%

Stable Free Radical Polymerization Kinetics of Alkyl Acrylate Monomers Using in situ FTIR Spectroscopy: Influence of Hydroxyl‐Containing Monomers and Additives

Lizotte

Long

2004

Macro Chemistry & Physics

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Summary: The homopolymerization and copolymerization of various alkyl acrylate monomers was studied under stable free radical polymerization (SFRP) conditions using in situ FTIR spectroscopy to monitor polymerization kinetics. The IR absorbance corresponding to the CH deformation of the monomer (968 cm−1) was measured to determine monomer conversion in real‐time fashion. The monomer disappearance profiles were subsequently converted to pseudo‐first order kinetic plots. Altering the alkyl ester chain length and configuration did not reveal a significant trend in the resulting polymerization kinetics. However, addition of 2‐hydroxyethyl acrylate (HEA) to a polymerization of n‐butyl acrylate (nBA) substantially accelerated the rate of total monomer conversion, increasing the observed rate constant almost two times. 1H NMR spectroscopy also showed that the resulting HEA/nBA copolymers were enriched with the HEA monomer. Moreover, a similar but enhanced effect was also observed upon the addition of small amounts of dodecanol to an n‐butyl acrylate homopolymerization resulting in more than a doubling of the observed rate constant.Resonance forms associated with the DEPN nitroxide and stabilization resulting from hydrogen bonding.magnified imageResonance forms associated with the DEPN nitroxide and stabilization resulting from hydrogen bonding.

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Real-Time Monitoring of the Stable Free Radical Polymerization of Styrene via in-Situ Mid-Infrared Spectroscopy

Cited by 45 publications

References 20 publications

Structure–property relationship of pH‐sensitive (PCL)₂(PDEA‐b‐PPEGMA)₂ micelles: Experiment and DPD simulation

Structure–property relationship of pH‐sensitive (PCL)₂(PDEA‐b‐PPEGMA)₂ micelles: Experiment and DPD simulation

Kinetic Studies of Metallocene‐Catalyzed Copolymerization of Propene with 10‐Undecene‐1‐ol Using In‐Line FTIR Spectroscopy

Stable Free Radical Polymerization Kinetics of Alkyl Acrylate Monomers Using in situ FTIR Spectroscopy: Influence of Hydroxyl‐Containing Monomers and Additives

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Real-Time Monitoring of the Stable Free Radical Polymerization of Styrene via in-Situ Mid-Infrared Spectroscopy

Cited by 45 publications

References 20 publications

Structure–property relationship of pH‐sensitive (PCL)2(PDEA‐b‐PPEGMA)2 micelles: Experiment and DPD simulation

Structure–property relationship of pH‐sensitive (PCL)2(PDEA‐b‐PPEGMA)2 micelles: Experiment and DPD simulation

Kinetic Studies of Metallocene‐Catalyzed Copolymerization of Propene with 10‐Undecene‐1‐ol Using In‐Line FTIR Spectroscopy

Stable Free Radical Polymerization Kinetics of Alkyl Acrylate Monomers Using in situ FTIR Spectroscopy: Influence of Hydroxyl‐Containing Monomers and Additives

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Structure–property relationship of pH‐sensitive (PCL)₂(PDEA‐b‐PPEGMA)₂ micelles: Experiment and DPD simulation

Structure–property relationship of pH‐sensitive (PCL)₂(PDEA‐b‐PPEGMA)₂ micelles: Experiment and DPD simulation