On the interaction mechanism of radical photoinitiators with monomers

Lemee, V.; Burget, Dominique; Jacques, Patrice; Fouassier, Jean‐Pierre

doi:10.1002/(sici)1099-0518(20000515)38:10<1785::aid-pola630>3.0.co;2-a

Cited by 20 publications

(27 citation statements)

References 29 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…The quenching of a triplet state by the monomer usually competes with the production of radicals. For 3 BP/TMPTA, a quenching rate constant of 7 × 10 7 M −1 s −1 was reported elsewhere 40. Taking into account the respective monomer and acetal concentrations, the 3 BP/monomer interaction is expected as the major 3 BP deactivation pathway when using BDA ( $k_{\rm q}^\prime$ [TMPTA] ∼ 3 × 10 8 s −1 > k q [BDA] ∼ 1 × 10 6 s −1 ) but not when BDA is change for BDO, PA, and MDN ( k q [BDO] ∼ 2 × 10 7 s −1 ; k q [PA] ∼ 6 × 10 7 s −1 ; k q [MDN] ∼ 7 × 10 8 s −1 ).…”

Section: Resultsmentioning

confidence: 74%

Photoinitiation mechanism of free radical photopolymerization in the presence of cyclic acetals and related compounds

Xiao

Lalevée

Allonas

et al. 2010

J. Polym. Sci. A Polym. Chem.

View full text Add to dashboard Cite

The behavior of six cyclic acetals and related compounds in the photoinitiation step of a radical photopolymerization was investigated. As shown by the photopolymerization kinetic data obtained from FTIR spectroscopy, most of them are efficient coinitiators in the presence of benzophenone (BP) with efficiencies close to a reference amine coinitiator (ethyl dimethylaminobenzoate, EDB). Laser flash photolysis and ESR spin trapping technique were used to study the photochemical mechanisms of the production of initiating radicals and explain the differences in reactivity. V C 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 5758-5766, 2010

show abstract

Section: Resultsmentioning

confidence: 74%

Photoinitiation mechanism of free radical photopolymerization in the presence of cyclic acetals and related compounds

Xiao

Lalevée

Allonas

et al. 2010

J. Polym. Sci. A Polym. Chem.

View full text Add to dashboard Cite

show abstract

“…The deactivation of aromatic ketones by acrylates is known to occur with relatively low rate constants (5.4 × 10 7 and 1.5 × 10 7 mol L −1 s −1 for the quenching of the triplet state of benzophenone and thioxanthone by methyl methacrylate, respectively) . The direct hydrogen transfer from MMA to benzophenone triplet state was suspected in, although this reaction was ruled out in a more recent paper . Besides this possible hydrogen transfer reaction, the possible formation of a 1,4‐biradical between the ketone triplet state and the monomer was pointed out as the main reaction pathway .…”

Section: Resultsmentioning

confidence: 99%

“…63 This assumption was further supported by semi-empirical calculations showing that (i) the thermodynamics of the process depends on the ketone triplet state energy and (ii) a nice relationship can be drawn between the quenching rate constant and the ketone triplet state energy. 64 Hence, the 1,4-biradical is expected to be involved in the polymerization reaction, in a quite similar way as the acrylate triplet state (Fig. 11).…”

Section: Self-initiation Mechanism Of Acrylate and Methacrylate Monomermentioning

confidence: 94%

“…benzophenone triplet state was suspected in, 63 although this reaction was ruled out in a more recent paper. 64 Besides this possible hydrogen transfer reaction, the possible formation of a 1,4-biradical between the ketone triplet state and the monomer was pointed out as the main reaction pathway. 63 This assumption was further supported by semi-empirical calculations showing that (i) the thermodynamics of the process depends on the ketone triplet state energy and (ii) a nice relationship can be drawn between the quenching rate constant and the ketone triplet state energy.…”

Section: Self-initiation Mechanism Of Acrylate and Methacrylate Monomermentioning

confidence: 99%

See 1 more Smart Citation

Acrylate nanolatex via self-initiated photopolymerization

Jasinski

Lobry

Lefevre

et al. 2014

J. Polym. Sci. Part A: Polym. Chem.

View full text Add to dashboard Cite

The use of UV light to initiate emulsion polymerization processes is generally overlooked, whilst extensive literature exists on photocuring of monomer films. In this study, the unique potential of UV light to produce at ambient temperature polyacrylate latexes without initiator was exploited. Although radical initiators are utilized at low concentration, their cost, toxicity, and odor provide incentives for finding alternatives. Starting with concentrated (30 wt %) and low scattering acrylate miniemulsions (droplet diameter <100 nm), it was demonstrated that acrylate self‐initiation can promote an efficient and fast photopolymerization in micrometer‐scale reactor (spectrophotometric cell) and lab‐scale photoreactor. Herein, all kinetic, colloidal, and mechanistic aspects involved in the self‐initiation of acrylate miniemulsion were extensively examined to provide a complete picture. In particular, the effects of droplet size, initiating wavelength, optical path, and irradiance on the course of the polymerization were thoroughly discussed. A diradical self‐initiation pathway is the most likely mechanism. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 1843–1853

show abstract

“…Upon absorption of UV‐radiation, the HCAP produces benzoyl and cyclohexyl radicals (denoted as P) by α‐cleavage at CC bonds (Scheme a) 12, 13. The resultant radicals formed by the cleavage of HCAP can abstract hydrogen atoms from the jute‐cellulose (Cell–H) and create active sites (Scheme b).…”

Section: Resultsmentioning

confidence: 99%

UV‐radiation‐induced preirradiation graft copolymerization of methacrylic acid and acrylic acid onto jute fibre

Khan¹

2004

Polymer International

View full text Add to dashboard Cite

UV-radiation-induced graft copolymerization of methacrylic acid and acrylic acid onto jute fibre was carried out using a preirradiation method with 1-hydroxycyclohexyl-phenylketone as a photoinitiator. 2-methyl-2-propene 1-sulfonic acid, sodium salt was incorporated into the grafting solution in suppressing the homopolymer/gel formation and facilitating graft copolymerization. In comparison, results showed that the type of monomer significantly influence on grafting. The results of the characterisation showed that the graft weight and the type of monomer have significant influence on the mechanical and water absorption properties in the case of grafted samples.

show abstract

On the interaction mechanism of radical photoinitiators with monomers

Cited by 20 publications

References 29 publications

Photoinitiation mechanism of free radical photopolymerization in the presence of cyclic acetals and related compounds

Photoinitiation mechanism of free radical photopolymerization in the presence of cyclic acetals and related compounds

Acrylate nanolatex via self-initiated photopolymerization

UV‐radiation‐induced preirradiation graft copolymerization of methacrylic acid and acrylic acid onto jute fibre

Contact Info

Product

Resources

About