Fluorothiocarbonyl compounds. VI. Free‐radical polymerization of thiocarbonyl fluoride
Abstract
Thiocarbonyl fluoride, CF 2S, and thiocarbonyl chlorofluoride, CFClS, undergo addition polymerization in free radical‐initiated systems. In addition, both compounds copolymerize with various unsaturated compounds, including typical vinyl and vinylidene monomers. The chlorofluoride, because of its rapid polymerization rate, copolymerizes best with very active monomers, of which 2,3‐dichloro‐1,3‐butadiene is an example. Thiocarbonyl fluoride polymerizes best at low temperatures. The trialkylborane—oxygen redox couple has been adapted to free‐radical polymerizations and copolymerizations from −60 to −120°C. With such initiation CF 2S has been copolymerized with terminal and internal olefins, vinyl compounds, allyl compounds, and acrylic esters. Copolymerization with propylene is unusual, in that it proceeds in a manner that strongly favors a product composed of two molecules of CF 2S for each propylene. In other cases, product compositions are more responsive to the ratio of monomers charged.
Integrity signals
Registry
Cites
Statistics
Claims the paper makes
Claims other papers make about this one
Each is checked against this paper’s own text: does it say what the citing paper says it does?
The polymerizations of fluorinated thiocarbonyl monomers typically required very low temperatures (−78 to −120 °C).
“The polymerizations typically required very low temperatures (−78 to −120 °C).”
From Direct Radical Copolymerizations of Thioamides To Generate Vinyl Polymers with Degradable Thioether Bonds in the Backbones (2023) · cites this paper as [36]
A pioneering report on radical polymerizations of fluorinated thiocarbonyl monomers such as S=CF2 and S=CClF was published in 1967 by Sharkey et al.
“A pioneering report was published in 1967 by Sharkey et al. on radical polymerizations of fluorinated thiocarbonyl monomers such as S=CF2 and S=CClF.36”
From Direct Radical Copolymerizations of Thioamides To Generate Vinyl Polymers with Degradable Thioether Bonds in the Backbones (2023) · cites this paper as [36]
Direct radical addition polymerizations of thiocarbonyl compounds have rarely been reported.
“Nevertheless, direct radical addition polymerizations of thiocarbonyl compounds have rarely been reported.”
From Direct Radical Copolymerizations of Thioamides To Generate Vinyl Polymers with Degradable Thioether Bonds in the Backbones (2023) · cites this paper as [36]
The syntheses and handling of fluorinated thiocarbonyl monomers were cumbersome.
“However, the syntheses and handling of these unique monomers were cumbersome.”
From Direct Radical Copolymerizations of Thioamides To Generate Vinyl Polymers with Degradable Thioether Bonds in the Backbones (2023) · cites this paper as [36]
Cites
Fluorothiocarbonyl Compounds. 1 I. Preparation of Thio Ketones, Thioacyl Halides, and Thio Esters
Middleton, W. J., Howard, E. G., & Sharkey, W. H. (1965) · The Journal of Organic Chemistry · doi:10.1021/jo01016a008 · Cited by 168 · see citing works
Self-citationThe mechanism of vinyl polymerization initiated by metal alkyls: Copolymerization studies
Zutty, N. L., & Welch, F. J. (1960) · Journal of Polymer Science · doi:10.1002/pol.1960.1204314214 · Cited by 72 · see citing works
Oxygen compounds as cocatalyst for triethylboron‐catalyzed vinyl polymerization
Furukawa, J., & Tsuruta, T. (1958) · Journal of Polymer Science · doi:10.1002/pol.1958.1202811623 · Cited by 58 · see citing works
FORMATION OF AN ORGANO BORON PEROXIDE BY REACTION OF OXYGEN AND TRIMETHYLBORANE1
Petry, R. C., & Verhoek, F. H. (1956) · Journal of the American Chemical Society · doi:10.1021/ja01605a038 · Cited by 39 · see citing works
Mechanism of trialkylboron initiated polymerization
Fordham, J. W. L., & Sturm, C. L. (1958) · Journal of Polymer Science · doi:10.1002/pol.1958.1203312654 · Cited by 38 · see citing works
Fluorothiocarbonyl compounds. V. Polymerization of thiocarbonyl compounds
Middleton, W. J., Jacobson, H. W., Putnam, R. E., et al. (1965) · Journal of Polymer Science Part A General Papers · doi:10.1002/pol.1965.100031208 · Cited by 11 · see citing works
Self-citation
Flagged first, then by citations
Cited by
Sorted by citations
Thiocarbonyl chemistry in polymer science
Bingham, N. M., Abousalman-Rezvani, Z., Collins, K., & Roth, P. J. (2022) · Polymer Chemistry · doi:10.1039/d2py00050d · Cited by 66 · see citing works
Watanabe, H., & Kamigaito, M. (2023) · Journal of the American Chemical Society · doi:10.1021/jacs.3c01796 · Cited by 51 · see citing works
- Authors
- Barney, A. L., Bruce, J. M., Coker, J. N., Jacobson, H. W., & Sharkey, W. H.
- Affiliations
- DuPont (United States) (US)
- ORCID
- Barney, A. L.
- Venue
- Journal of Polymer Science Part A-1: Polymer Chemistry
- Publisher
- Wiley
- Published
- 1966-10
- Volume
- 4
- Issue
- 10
- Pages
- 2617-2636
- ISSN
- 0449-296X (ISSN-L)
- 1542-9350
- OpenAlex
- W2004315348
- Cited by
- 23
- References
- 6
- Citations by year
- 2023: 3 · 2022: 2 · 2021: 1 · 2015: 1 · 2012: 1
- FWCI
- 2.08
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Journal of Polymer Science Part A-1 Polymer Chemistry (publishedVersion)
- Topics
- Physical Sciences › Chemistry › Organic Chemistry › Advanced Polymer Synthesis and Characterization
- Physical Sciences › Materials Science › Polymers and Plastics › Synthesis and properties of polymers
- Physical Sciences › Chemistry › Organic Chemistry › Photopolymerization techniques and applications
- Keywords
- radical polymerization, copolymerization, addition polymerization, vinyl monomers, low-temperature polymerization, propylene copolymerization
About these checks
Registry, retraction, Cites and statistics results are computed, not judged, with one exception: a printed reference that no index lists is read once by a model before it counts as a citation error. Claims are extracted by a model and kept only when their quote appears verbatim in the text; each cited source is then checked, with a model’s help, for whether it says what the claim relies on. Those verdicts can be wrong — read the claim’s quote and the cited source before relying on one.
Statistics and arithmetic are recomputed, not judged.
Confidence bands are shown only for fields calibrated on our annotated test set. None is calibrated yet, so no band is shown.
What counts as a claim ›How we measure confidence ›How we check this ›
Are you an author, or do you see a problem with this page? Request a review
