Synthesis of polycarbonates by a silicon-assisted alkoxy/carbonylimidazolide coupling reaction

Bolton, Daniel H.; Wooley, Karen L.

doi:10.1002/(sici)1099-0518(19970430)35:6<1133::aid-pola16>3.0.co;2-7

Cited by 7 publications

(3 citation statements)

References 2 publications

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“…[8] For example, in 1983, Kricheldorf introduced the "silyl method" for the synthesis of polyaryl ethers taking advantage of the strength of the Si-F bond and the innocuous nature of the silyl fluoride byproducts. [9] In 2008, Gembus demonstrated that sulfonyl fluorides react with silyl ethers in the presence of a catalytic amount of DBU (eq.…”

Section: Hhs Public Accessmentioning

confidence: 70%

SuFEx‐Based Synthesis of Polysulfates

et al. 2014

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A handful of high fidelity reactions are at the core of industrial processes producing polymers in multimillion-ton quantities. Most commodity polymers are synthesized from olefins by forming carbon-carbon backbones, whereas engineering polymers are commonly prepared via condensation reactions of monomers often containing an activated carbonyl group or its equivalent and a suitable nucleophile, thus forming carbon-heteroatom linkages. Polyesters, polyamides, polyurethanes, and polyimides are produced in this manner. Despite the variety of backbone structures, polymers containing sulfur(VI) "-SO 2 -" connectors are virtually absent from the literature and are barely used in industrial applications (with the exception of polysulfones, in which the sulfone group is already present in the monomers [1] ).Unsurprisingly, most reported attempts to synthesize sulfur(VI)-containing polymers relied on reactions mimicking carbonyl group-based condensations, i.e. reactions of sulfonyl chlorides with nucleophiles [2] and, to a much lesser extent, Friedel-Crafts sulfonylations. [3] While polymers obtained by those methods can have attractive properties, such as good thermal and hydrolytic stability and mechanical resilience, [2c-e] the unselective reactivity of sulfur(VI) chlorides, which are susceptible to hydrolysis and participate in redox transformations and radical chlorinations, significantly limit the utility of these methods and materials.Sulfur(VI) fluorides, in particular sulfuryl fluoride (SO 2 F 2 ) and its monofluorinated derivatives, sulfonyl (RSO 2 -F) fluorides, sulfamoyl (R 2 NSO 2 -F) fluorides, and fluorosulfates (ROSO 2 -F) stand in stark contrast to other sulfur(VI) halides. These sulfur oxofluorides are much more hydrolytically stable, redox silent, and do not act as halogenating agents. Nevertheless, their selective reactivity can be revealed when an * fokin@scripps.edu Homepage: http://www.scripps.edu/fokin; sharples@scripps.edu Homepage: http://www.scripps.edu/sharpless. Supporting information for this article is available on the WWW under http://www.angewandte.org or from the authors. The formation of sulfonyl-heteroatom bonds is described in detail in an accompanying article in this issue. [5] In the early 1970s, Firth pioneered the synthesis of poly(arylsulfate) polymers from fluorosulfates of Bisphenol A (BPA), which he obtained from SO 2 F 2 , and disodium salts of the bisphenol. [6] Preparation of these monomers required prolonged heating, and pure high polymer was obtained only after repeated precipitation. Here, we report a simple and straightforward SuFEx-based method for the synthesis of high molecular weight polysulfate polymers from aryl fluorosulfates and aryl silyl ethers under simple and mild reaction conditions. HHS Public AccessReactions of silylated and fluorinated compounds are, of course, well known in organic synthesis [7] and in polymer chemistry. [8] For example, in 1983, Kricheldorf introduced the "silyl method" for the synthesis of polyaryl ethers taking advantage of the str...

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Section: Hhs Public Accessmentioning

confidence: 70%

SuFEx‐Based Synthesis of Polysulfates

et al. 2014

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“…[8] For example, in 1983, Kricheldorf introduced the “silyl method” for the synthesis of polyaryl ethers taking advantage of the strength of the Si–F bond and the innocuous nature of the silyl fluoride byproducts. [9] In 2008, Gembus demonstrated that sulfonyl fluorides react with silyl ethers in the presence of a catalytic amount of DBU (eq.…”

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confidence: 99%

SuFEx‐Based Synthesis of Polysulfates

et al. 2014

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High‐molecular‐weight polysulfates are readily formed from aromatic bis(silyl ethers) and bis(fluorosulfates) in the presence of a base catalyst. The reaction is fast and proceeds well under neat conditions or in solvents, such as dimethyl formamide or N‐methylpyrrolidone, to provide the desired polymers in nearly quantitative yield. These polymers are more resistant to chemical degradation than their polycarbonate analogues and exhibit excellent mechanical, optical, and oxygen‐barrier properties.

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“…23 Furthermore, the efficient formation of linear carbonate bonds has been achieved through the substitution reaction of intermediary acylimidazole and silyl alkoxide. 22 These results led us to examine the ring-opening polymerization with the use of IM derivatives as catalysts for grafting from PSQ. The synthetic route is shown in Scheme 1.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of grafted polysilsesquioxane by ring-opening polymerization of lactide and trimethylene carbonate

Kashio

Sugizaki

Tanaka

et al. 2011

Polym J

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The polysilsesquioxane (PSQ) containing 3-aminopropyl and phenyl groups (APSQ) was prepared from the corresponding trimethoxysilanes by co-condensation under basic conditions. The amino groups on APSQ were used as the initiator species for the graft polymerization of 1,3-trimethylene carbonate (TMC) and L-(-)-lactide (LA). The ring-opening polymerization of TMC and LA in the presence of the catalytic 1-trimethylsilylimidazole proceeded effectively to afford the PSQ with poly(TMC) and/or poly(LA) as the graft chains. The grafted PSQ containing poly(LA) showed the heat durability as an advantage of the hybrid polymer. In differential scanning calorimetry analysis, the grafted random copolymer of TMC and LA showed no clear endotherm corresponding to melting point (T m ). For the poly(LA)-grafted PSQ, the peak indicating T m was observed in the first heating run, but the corresponding peak was very small in the second run.

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Synthesis of polycarbonates by a silicon-assisted alkoxy/carbonylimidazolide coupling reaction

Cited by 7 publications

References 2 publications

SuFEx‐Based Synthesis of Polysulfates

SuFEx‐Based Synthesis of Polysulfates

SuFEx‐Based Synthesis of Polysulfates

Synthesis of grafted polysilsesquioxane by ring-opening polymerization of lactide and trimethylene carbonate

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