Kinetic study of free-radical polymerization photoinitiated by cyanine-borate salts. II.

Kabatc, Janina; Jędrzejewska, Beata; Pączkowski, Jerzy

doi:10.1002/1099-0518(20000701)38:13<2365::aid-pola90>3.0.co;2-8

Cited by 22 publications

(8 citation statements)

References 17 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The mechanism of photoinitiation, consistent with Schuster and coworkers 4–6. observations for cyanine–alkyltriphenylborate photoredox pairs has been previously suggested 23. Electron transfer from the borate anion to the singlet excited state of cyanine dye molecule leads to the formation of cyanine radical and boranyl radical which rapidly decomposes producing an alkyl radical.…”

Section: Resultssupporting

confidence: 85%

“…Recently, we reported that the carbocyanine dyes borate salts act as efficient photoinitiators that are able to satisfy the requirements in the field of photopolymerization 22–24. Generally, the photoinitiating abilities of such photoinitiator systems are less effective than the photoinitiating ability of dyeing photoinitiating photoredox pair in which, after irradiation with visible light the long‐lived excited triplet state of dye is formed.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Three‐cationic carbocyanine dyes as sensitizers in very efficient photoinitiating systems for multifunctional monomer polymerization

Kabatc¹,

Pączkowski²

2009

J. Polym. Sci. A Polym. Chem.

Self Cite

View full text Add to dashboard Cite

This article is focused on the description of the synthesis, spectroscopic, electrochemical properties, and the free radical photoinitiation abilities of new threecationic carbocyanine dyes. A new synthestic strategy for preparation of symmetrical cyanine dyes has been developed based on the 2-methylbenzothiazole, 2-methylbenzoxazole and 2,3,3-trimethylindolinium quaternization by a-bromo-x-tertiary ammonium salts followed by the condensation of obtained product with triethyl ortho-formate. Resulted dyes possess in one molecule three quaternary nitrogen atoms, for example, they are three-cationic in character. Novel three-cationic symmetric carbocyanine dyes paired with n-butyltriphenylborate anions are very efficient photoinitiators of free radical polymerization of acrylate monomers, for example, (TMPTA) when irradiated with the visible emission of an argon-ion laser. The photoinitiating abilities of the novel photoredox pairs were compared to the photoinitiation properties of their monocationic equivalents, for example, N,N 0 -diethylthia-, N,N 0 -diethyloxa-and N,N 0 -dimethylindocarbocyanine n-butyltriphenylborates (SB2, OB2, and IB2) and also compared to the initiation ability of Rose Bengal derivative, for example, typical triplet state photoinitiator. The kinetic studies clearly demonstrated that the three-cationic carbocyanine borate photoredox pairs exhibit a significant increase in the efficiency of TMPTA free radical polymerization in comparison to the photoredox pairs containing structurally related, mono-cationic carbocyanine borates. It was also shown that, the addition of a second coinitiator to the cyanine borate salts enhances their photoinitiating abilities. The best results were obtained for three cationic carbocyanine borates in the presence of second coinitiator being N-methoxypyridinium n-butyltriphenylborate. The photoinitiating abilities of the systems of these types are more effective than those composed of carbocyanine cation/borate anion exclusively. V V C 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: [4636][4637][4638][4639][4640][4641][4642][4643][4644][4645][4646][4647][4648][4649][4650][4651][4652][4653][4654] 2009

show abstract

Section: Resultssupporting

confidence: 85%

Section: Introductionmentioning

confidence: 99%

Three‐cationic carbocyanine dyes as sensitizers in very efficient photoinitiating systems for multifunctional monomer polymerization

Kabatc¹,

Pączkowski²

2009

J. Polym. Sci. A Polym. Chem.

Self Cite

View full text Add to dashboard Cite

show abstract

“…It is demonstrated that 8 isomers are available for this cationic cyanine dye, and that the most stable entgegen conformer E1 represents more than 92% of the ground state population at 20 1C. Molecular modeling also rules out any cyclization mechanism in AO-R, contrary to well-known merocyanine-spyropirane dyes, [17][18][19][20][21][22][23][24][25] due to steric hindrance. Associating computational results and experimental data permit to identify the formed photoproduct as one of the Z isomers and allow us to postulate a possible mechanism in which two isomerizations could be involved: a very fast one, and a slower, viscosity-dependent one, which governs AO-R fluorescence lifetime.…”

Section: Discussionmentioning

confidence: 99%

“…9,10 While the merocyanines are very famous for their photochromic behavior, [11][12][13][14] some other cyanines present interesting reactivity in the field of radical photogeneration. [15][16][17][18] After light absorption, the dyes go into their excited state from where they can deactivate towards triplets states, begin a fragmentation reaction, react with other molecules either by energy transfer or electron transfer. These mechanisms are very important because they determine the reactivity and efficiency of the photochemistry of the dye.…”

Section: Introductionmentioning

confidence: 99%

Joint spectroscopic and theoretical investigation of cationic cyanine dye Astrazon Orange-R: solvent viscosity controlled relaxation of excited states

Ley

Bordat

Stefano

et al. 2015

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

In this paper, the first study of cationic cyanine dye Astrazon Orange-R by combined spectroscopic and theoretical investigation is presented. It is shown that molecular modeling of Astrazon Orange-R is in very good agreement with experiment, allowing us to gain insight into its complicated photophysics. A solvent viscosity controlled relaxation of excited states, involving cyanine isomerization, is also outlined.

show abstract

“…Some combinations of organoborate salts and cationic chromophores are well known to serve as effective radical photoinitiators in the UV or visible‐light region 1–4. A cationic cyanine–borate complex can even act as an infrared photoinitiator 5.…”

Section: Introductionmentioning

confidence: 99%

Vinyl polymerization with a binary system of p‐chlorobenzenediazonium salt and sodium tetraphenylborate

Sato

Takahashi

Seno

et al. 2001

J. Polym. Sci. A Polym. Chem.

View full text Add to dashboard Cite

A combined system of sodium tetraphenylborate (STPB) and p-chlorobenzenediazonium tetrafluoroborate (CDF) serves as an effective initiator at low temperatures for acrylate monomers such as methyl methacrylate (MMA), ethyl acrylate, and di-2-ethylhexyl itaconate. The polymerization of MMA with the STPB/CDF system has been kinetically investigated in acetone. The polymerization shows a low overall activation energy of 60.3 kJ/mol. The polymerization rate (R p ) at 40°C is given by R p ϭ k[STPB/CDF] 0.5 [MMA] 1.6 , when the molar ratio of STPB to CDF is kept constant at unity, suggesting that STPB and CDF form a complex with a large stability constant and play an important role in initiation and that MMA participates in the initiation process. From the results of a spin trapping study, p-chlorophenyl and phenyl radicals are presumed to be generated in the polymerization system. A plausible initiation mechanism is proposed on the basis of kinetic and electron spin resonance results. A large solvent effect on the polymerization can be observed. The largest R p value in dimethyl sulfoxide is 11 times the smallest value in N,N-dimethylformamide. The copolymerization of MMA and styrene with the STPB/CDF system gives results somewhat different from those of conventional radical copolymerization.

show abstract

Kinetic study of free-radical polymerization photoinitiated by cyanine-borate salts. II.

Cited by 22 publications

References 17 publications

Three‐cationic carbocyanine dyes as sensitizers in very efficient photoinitiating systems for multifunctional monomer polymerization

Three‐cationic carbocyanine dyes as sensitizers in very efficient photoinitiating systems for multifunctional monomer polymerization

Joint spectroscopic and theoretical investigation of cationic cyanine dye Astrazon Orange-R: solvent viscosity controlled relaxation of excited states

Vinyl polymerization with a binary system of p‐chlorobenzenediazonium salt and sodium tetraphenylborate

Contact Info

Product

Resources

About