Free radical copolymerization behavior of methyl α-(trifluoromethyl)acrylate and α-(trifluoromethyl)acrylonitrile: penultimate monomer unit effect and monomer reactivity parameters

Iwatsuki, Shouji; Kondo, Akihiro; Harashina, Hatsuhiko

doi:10.1021/ma00142a004

Cited by 47 publications

(19 citation statements)

References 3 publications

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“…Extrapolation to E = 0 and E = 1 affords values of N = À(r 2 /a) and r 1 , respectively. The values of r 1 and r 2 obtained from this procedure were found to be 0.15 and 0.98, respectively and the value of r 1 r 2 was [11]. The obtained values of r 1 , r 2 and r 1 r 2 reveal that the two monomer species are randomly distributed in the yielded copolymer.…”

mentioning

confidence: 74%

Preparation and properties of two-component hydrogels based on 2-acrylamido-2-methylpropane sulphonic acid

Abdel‐Azim

Farahat

Atta

et al. 1998

Polym. Adv. Technol.

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mentioning

confidence: 74%

Preparation and properties of two-component hydrogels based on 2-acrylamido-2-methylpropane sulphonic acid

Abdel‐Azim

Farahat

Atta

et al. 1998

Polym. Adv. Technol.

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“…In contrast to those above investigations concerning the radical copolymerization of α‐trifluoromethacrylates, only a few reports on ionic polymerization are available 41, 42. For example, TBTFMA and TFMAA have been successfully homopolymerized by anionic polymerization 43, 44. Typical anionic initiators for methyl methacrylate (MMA) polymerizations gave rise to complications such as attack on the trifluoromethyl moiety.…”

Section: Introductionmentioning

confidence: 99%

Kinetics of the radical copolymerization of 2,2,2‐trifluoroethyl methacrylate with tert‐butyl α‐trifluoromethacrylate

Boschet¹,

Kostov²,

Améduri³

et al. 2010

J. Polym. Sci. A Polym. Chem.

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The radical copolymerization of two different methacrylate monomers, 2,2,2‐trifluoroethyl methacrylate (TFEMA) and tert‐butyl α‐trifluoromethacrylate (TBTFMA) in solution was investigated. The resulting statistic poly(TFEMA‐co‐TBTFMA) copolymers were characterized by NMR spectroscopy to assess their compositions. The kinetics of copolymerization enabled one to determine the reactivity ratios of both comonomers according to the methods of Fineman‐Ross, Kelen‐Tüdos, and extended Kelen‐Tüdos. Excellent correlations were found between these methods leading to the following reactivity ratios: rTFEMA = 4.87 ± 1.50 and rTBTFMA = 0.10 ± 0.02 at 74 °C. These values indicated that the structure of the copolymers was composed of poly(TFEMA) micro‐blocks separated by one TBTFMA unit. Both yields and molecular weights (ranging between 1,000 and 12,000 g/mol) increased with the TFEMA content. The thermal stability of these (co)polymers showed that the decomposition temperature at 10% weight loss increased both with TFEMA content and increasing molecular weights of the poly(TFEMA‐co‐TBTFMA) copolymers. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1029–1037, 2010

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“…They have reported that the e-value of MTFMA is as high as 2.5 and Q = 0.74 by the mercury method 30) . Shortly after the report, Iwatsuki et al reported their results on radical copolymerization of MTFMA with the monomers such as p-chlorostyrene, styrene and MMA by bulk polymerization initiated with AIBN 31) . The monomer reactivity ratios MTFMA (M 1 ) with MMA (M 2 ) are r 1 = 0.1 l 0.1 and r 2 = 2.3 l 0.2.…”

Section: On the Polymerization Reactivity Of Atrifluoromethylvinyl Comentioning

confidence: 99%

“…The estimated Q, e-values of MTFMA are Q = 0.8 and e = 2.9, which is clear evidence that the reactivity of the vinyl group is strongly affected by the a-trifluoromethyl group. Iwatsuki et al also reported the difficulty to polymerize MTFMA since the radical homopolymerization produced the polymer although the yields were less than 20% 31) . 32) since the e-value of ETFMA should be as high as that of MTFMA.…”

Section: On the Polymerization Reactivity Of Atrifluoromethylvinyl Comentioning

confidence: 99%

On the polymerization reactivity of fluorinated vinyl monomers

Narita¹

2000

Macromol. Rapid Commun.

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The polymerization reactivities of α,β,β‐trifluorovinyl compounds (CF2=CF—R) and α‐trifluoromethylvinyl compounds (CH2=C(CF3)—R) are discussed since these monomers have scarcely been investigated and hardly yielded corresponding homopolymers, although tetrafluoroethylene and chlorotrifluoroethylene have been studied under radical polymerization conditions. In the case of α,β,β‐trifluorostyrene, a homopolymer is obtained in low yields by anionic polymerization and it is concluded that the reaction takes place without any side reactions once the reaction has started, since simple addition polymerization is observed and the molecular weight distribution is very narrow. Anionic polymerization of hexafluorobuta‐1,3‐diene is successfully achieved by the addition reaction of living end to the 2‐carbon of hexafluorobuta‐1,3‐diene followed by isomerization to produce excellently high thermostable polymers. ω‐Trifluorovinyloxyfluoroalkyl alcohol produces a polyether via a polyaddition reaction under anionic conditions. The homopolymers of α‐trifluoromethylacrylates are quantitatively obtained under anionic polymerization conditions. α‐Trifluoromethylstyrene derivatives are likely to polymerize under radical conditions, but are not well‐studied. The radical polyaddition reaction of perfluoroisopropenyl esters in 1,4‐dioxane, diethyl ether or 1,2‐dimethoxyethane yields the polymers possessing the solvent moiety in the polymer main chain, respectively. It is clearly demonstrated that each fluorinated vinyl monomer discussed in this article demands its own reaction conditions. Therefore, more experimental data on the polymerization of these individual monomers is needed, including research on developing the reactions discovered in the organofluorine chemistry field to the preparation of polymers.

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Free radical copolymerization behavior of methyl α-(trifluoromethyl)acrylate and α-(trifluoromethyl)acrylonitrile: penultimate monomer unit effect and monomer reactivity parameters

Cited by 47 publications

References 3 publications

Preparation and properties of two-component hydrogels based on 2-acrylamido-2-methylpropane sulphonic acid

Preparation and properties of two-component hydrogels based on 2-acrylamido-2-methylpropane sulphonic acid

Kinetics of the radical copolymerization of 2,2,2‐trifluoroethyl methacrylate with tert‐butyl α‐trifluoromethacrylate

On the polymerization reactivity of fluorinated vinyl monomers

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