Initiating free radical polymerization

Moad, Graeme; Chiefari, John; Mayadunne, Roshan T. A.; Moad, Catherine L.; Postma, Almar; Rizzardo, Ezio; Thang, San H.

doi:10.1002/1521-3900(200206)182:1<65::aid-masy65>3.0.co;2-e

Cited by 101 publications

(164 citation statements)

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“…Bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide (2) and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (3) (Ciba Specialty Chemicals) were recrystallized from ethanol. 2-Hydroxy-2-methyl-1-phenylpropan-1-one (4) (Ciba Specialty Chemicals), methyl acrylate (5), n-butyl acrylate (6), tert-butyl acrylate (7), vinyl acrylate (8), methyl methacrylate (9), and vinyl pivalate (10) (all from Aldrich) were used as received. HPLC-grade toluene from Aldrich and tetrahydrofuran (THF, inhibitor-free) from Acros were used as solvents without further purification.…”

Section: Methodsmentioning

confidence: 99%

“…In addition, radical addition reactions are important both in polymer chemistry and in organic synthesis; phosphorus-and carbon-centered radicals are widely used in these fields. [1][2][3][4][5][6][7][8][9][10][11] The reaction enthalpy of the addition step is a key factor in determining the rate of radical addition reactions. However, an interplay of steric, polar, and substituent effects, in addition to reaction enthalpy, can affect the rate constant of addition to a double bond.…”

Section: Introductionmentioning

confidence: 99%

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A Novel Approach for Measuring Absolute Rate Constants by Pulsed Electron Spin Resonance: Addition of Phosphinoyl and 2-Hydroxy-2-propyl Radicals to Several Alkenes^,

Weber

Turro

2003

J. Phys. Chem. A

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A time-resolved Fourier transform electron spin resonance (TR FT ESR) method for determining absolute rate constants of reactive, free radical reactions is described. The phase memory times T M of a family of reacting radicals were measured precisely by electron spin-echo (ESE) detection. In all cases the ESE signal decays show a simple pseudo-first-order behavior. Rate constants of the reactions were extracted from the linear relationship between the reciprocal of the T M values and the alkene concentrations. The validity of the method is demonstrated for the measurement of the rate constant for addition of different phosphinoyl and 2-hydroxy-2-propyl radicals to several acrylates, methyl methacrylate, and vinyl pivalate in organic solvents at room temperature. The results are in excellent agreement with those obtained by other kinetic investigations employing time-resolved steady-state electron spin resonance (TR CW ESR) and optical absorption spectroscopy. The technique is shown to be applicable to systems with rate constants between 10 4 and 10 8 M -1 s -1 , a range covered by the alkenes examined.

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

A Novel Approach for Measuring Absolute Rate Constants by Pulsed Electron Spin Resonance: Addition of Phosphinoyl and 2-Hydroxy-2-propyl Radicals to Several Alkenes^,

Weber

Turro

2003

J. Phys. Chem. A

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“…[8][9][10] Radical addition reactions have been an important area for research in free radical chemistry and in chemical kinetics. The interplay of steric, polar, and substituent effects, as well as reaction enthalpy, affect the rate of addition of a radical to a double bond.…”

Section: Introductionmentioning

confidence: 99%

Electron Spin Resonance and Laser Flash Photolysis Study of Radical Addition to Vinyl Acrylate and Related Alkenes

2001

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Addition of two radicals (diphenyl phosphinoyl and 2-hydroxy-2-propyl) to the bifunctional alkene, vinyl acrylate, was studied by both time-resolved (TR) and steady-state (SS) ESR and laser flash photolysis (LFP). The adduct radicals are predominately a result of tail addition (addition to the unsubstituted carbon atom) of the acrylate double bond. Chemical structures of the adducts were established by comparison of the observed ESR spectra with those of adducts of the same reactive radicals to structurally related alkenes, tert-butyl acrylate and vinyl pivalate, which have only one type of double bond. Adducts of bulky phosphinoyl radicals to the acrylates demonstrate hindered rotation and a cis-trans isomerization at room temperature. The structure of the adduct radicals and the reactivity of the two radicals are discussed. Absolute rate constants for the addition of the phosphinoyl radical to the alkenes were measured by LFP in ethyl acetate at 296 K. A rate constant of k add ) (33 ( 1) × 10 6 M -1 s -1 was found for vinyl acrylate. The latter value is ∼1.5 times higher than that for tert-butyl acrylate (k add ) (22 ( 1) × 10 6 M -1 s -1 ) and ∼17 times higher than that for vinyl pivalate (k add ) (2.0 ( 0.1) × 10 6 M -1 s -1 ). These rate constants are consistent with conclusions derived from the ESR data. The results provide some insights into free radical polymerization of vinyl acrylate and vinyl ethers.

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“…One of the most successful methods to make well-defined polymers is through atom transfer radical polymerization (ATRP) [1][2][3][4][5][6][7][8]. This method employs a redox process with transition metal complexes in which a halogen ion is transferred reversibly between the transition metal and the polymer chain end.…”

Section: Introductionmentioning

confidence: 99%

The electrochemical detection of Ru(II) in a methyl methacrylate solution

Wael

Adriaens

Temmerman

2006

Talanta

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This article describes the voltammetric behaviour of RuCl 2 (PPh 3 ) 3 in a methyl methacrylate (MMA) solution. Acquiring this type of information is only possible when the ohmic resistance can be kept sufficiently low. Therefore, the conductivity study of pure methyl methacrylate and a tetrabutylammonium tetrafluoroborate (TBABF 4 ) methyl methacrylate solution has been described as well. Impedance measurements show an increase in conductivity by adding TBABF 4 , while a conductometric curve illustrates the presence of ion pairs, triple ions and quadrupoles depending on the TBABF 4 concentration. The conductivity of a 0.1 mol L −1 TBABF 4 -MMA solution (formation of charged triple ions) was high enough to perform electrochemical experiments and a calibration curve could be obtained. The ability of obtaining relevant electrochemical data in low conducting media opens up new perspectives, especially for electroanalytical purposes used to monitor polymer reactions, more specific atom transfer radical polymerization (ATRP) reactions. This method employs a redox process with transition metal complexes in which a halogen ion is transferred reversibly between the transition metal and the polymer chain end. The dynamic equilibrium can be monitored by measuring the ruthenium concentration.

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Initiating free radical polymerization

Cited by 101 publications

References 0 publications

A Novel Approach for Measuring Absolute Rate Constants by Pulsed Electron Spin Resonance: Addition of Phosphinoyl and 2-Hydroxy-2-propyl Radicals to Several Alkenes^,

A Novel Approach for Measuring Absolute Rate Constants by Pulsed Electron Spin Resonance: Addition of Phosphinoyl and 2-Hydroxy-2-propyl Radicals to Several Alkenes^,

Electron Spin Resonance and Laser Flash Photolysis Study of Radical Addition to Vinyl Acrylate and Related Alkenes

The electrochemical detection of Ru(II) in a methyl methacrylate solution

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Initiating free radical polymerization

Cited by 101 publications

References 0 publications

A Novel Approach for Measuring Absolute Rate Constants by Pulsed Electron Spin Resonance: Addition of Phosphinoyl and 2-Hydroxy-2-propyl Radicals to Several Alkenes,

A Novel Approach for Measuring Absolute Rate Constants by Pulsed Electron Spin Resonance: Addition of Phosphinoyl and 2-Hydroxy-2-propyl Radicals to Several Alkenes,

Electron Spin Resonance and Laser Flash Photolysis Study of Radical Addition to Vinyl Acrylate and Related Alkenes

The electrochemical detection of Ru(II) in a methyl methacrylate solution

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A Novel Approach for Measuring Absolute Rate Constants by Pulsed Electron Spin Resonance: Addition of Phosphinoyl and 2-Hydroxy-2-propyl Radicals to Several Alkenes^,

A Novel Approach for Measuring Absolute Rate Constants by Pulsed Electron Spin Resonance: Addition of Phosphinoyl and 2-Hydroxy-2-propyl Radicals to Several Alkenes^,