N-Heterocyclic carbene-catalysed synthesis of polyurethanes

Coutelier, Olivier; Ezzi, Mohammad El; Destarac, Mathias; Bonnette, Fabien; Kato, Tsuyoshi; Baceiredo, Antoine; Sivasankarapillai, Gopakumar; Gnanou, Yves; Taton, Daniel

doi:10.1039/c2py00477a

Cited by 48 publications

(44 citation statements)

References 22 publications

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“…Attack by the NHC on the alcohol functionalities was revealed as the most probable initiation mechanism using NMR spectroscopic experiments. Free NHC 5‐tBu has also been used for the polymerization of various aliphatic diols and diisocyanates (Scheme (a)) . It was found that it was indeed possible to receive soluble, linear PUs (2000–5000 g mol −1 ), if linear aliphatic diisocyanates were applied; otherwise crosslinking side reactions occurred.…”

Section: Step‐growth Polymerizationsmentioning

confidence: 99%

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N‐Heterocyclic carbenes for metal‐free polymerization catalysis: an update

Naumann

Dove

2015

Polymer International

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This mini‐review is intended to serve as a concise introduction to polymerizations that are catalysed by N‐heterocyclic carbenes. The content is structured according to accessible monomer functionalities and type of polymerization. Both major achievements as well as the latest developments in this rapidly evolving field are presented. A broad range of different types of monomers is covered in this way, including among others lactones, epoxides, anhydrides, acrylates, siloxanes and lactams. Special emphasis is put on mechanistic understanding and structure–activity relationships. © 2015 Society of Chemical Industry

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Section: Step‐growth Polymerizationsmentioning

confidence: 99%

“…The study supports the alcohol‐activation pathway previously postulated by Buchmeiser and co‐workers and notably it was reported that the order of monomer addition was crucial. Mixing of 5‐tBu and isocyanates alone and subsequent addition of diols led to deactivation …”

Section: Step‐growth Polymerizationsmentioning

confidence: 99%

N‐Heterocyclic carbenes for metal‐free polymerization catalysis: an update

Naumann

Dove

2015

Polymer International

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“…described the catalytic activity of 1,3-bis-(di-tert-butyl)imidazole-2-ylidene (tBuNHC) for the polymerization of aliphatic diisocyanates and diols, using relatively low catalyst loading and mild conditions. [31] However, all these studies are exclusively devoted to Downloaded by [University of California, San Diego] at 04: 54 27 March 2016 acid and trifluoromethane sulfonic acid (triflic acid), as well as 1-methoxy-2-propanol (PGME) and di(propylene glycol) dimethyl ether (DPGDME) were purchased from Aldrich France. 1-butyl-2,3-dicyclohexyl-1-methylguanidine (Cy 2 MeBuG), 1-cyclohexyl-2,2,3,3-tetrapropylguanidine (CyPr 4 G), and 1-octyl-2,2,3,3-tetramethylguanidine (OctTMG) were synthesized by Bluestar Silicones (SaintFons, France).…”

Section: Introductionmentioning

confidence: 99%

Novel nucleophilic/basic and acidic organocatalysts for reaction between poorly reactive diisocyanate and diols

Belmokaddem

Dagonneau

Lhomme

et al. 2016

Designed Monomers and Polymers

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International audienceOriginal basic or acidic organic compounds derived from guanidine or phenyl phosphonic acid were specifically designed and tested as new catalysts for the bulk synthesis of polyurethane prepolymers from a precursor system with particularly low reactivity (secondary alcohol + aliphatic isocyanate at low temperature). Both families showed interesting catalytic activities at 60-80 degrees C, but must nevertheless be used in much higher amounts (1mol%, i.e. between 0.15 and 0.50wt%) than traditional metal-based catalysts. The efficiency of guanidine derivatives seems to be related to their nucleophilicity, whereas that of phosphonic acid derivatives depends on their acidity. However, the solubility of the considered species in the reactive medium also plays a major role. The water/alcohol selectivity of the catalysts, especially at room temperature, was then examined as an additional criterion. Guanidines are not selective and favor the reaction of isocyanate groups with water as much as that with alcohols. Phenyl phosphonic acid derivatives are more selective, and particularly pentafluorophenyl phosphonic acid displays a remarkable catalytic activity together with an acceptable selectivity and could represent an interesting and safer alternative to toxic tin and mercury derivatives for many industrial polyurethanes

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“…The utility of the NHC-mediated reactions has also been expanded to polymer synthesis (161,162), via predominantly the ROP of cyclic monomers, such as cyclic esters (163), epoxides (164,165), cyclic siloxanes (166), and N-carboxyl-anhydrides (167). NHC-catalyzed stepgrowth polymerization has been reported as well (168)(169)(170). Polymerization of α,β-unsaturated esters, such as MMA, has also been recently realized through the classic GTP initiated by SKAs (35,144,145), using NHCs as alternative nucleophilic catalysts to activate the acetal initiator (171,172).…”

Section: Zwitterionic Polymerizationmentioning

confidence: 99%

Sustainable Polymers from Biomass‐Derived α‐Methylene‐γ‐Butyrolactones

Gowda

Chen

2013

Encyclopedia of Polymer Science and Technology

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Sustainable polymers based on the biomass‐derived renewable α‐methylene‐γ‐butyrolactones, including α‐methylene‐γ‐butyrolactone, γ‐methyl‐α‐methylene‐γ‐butyrolactone, and β‐methyl‐α‐methylene‐γ‐butyrolactone, are reviewed. Polymerization methods employed for the synthesis of such polymers are classified into four different categories according to polymerization types or mechanisms: free radical polymerization, coordination polymerization, group‐transfer and anionic polymerization, and zwitterionic polymerization. In addition to synthetic methods, polymer properties, polymerization characteristics, as well as polymerization and stereochemical control mechanisms are also described.

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N-Heterocyclic carbene-catalysed synthesis of polyurethanes

Cited by 48 publications

References 22 publications

N‐Heterocyclic carbenes for metal‐free polymerization catalysis: an update

N‐Heterocyclic carbenes for metal‐free polymerization catalysis: an update

Novel nucleophilic/basic and acidic organocatalysts for reaction between poorly reactive diisocyanate and diols

Sustainable Polymers from Biomass‐Derived α‐Methylene‐γ‐Butyrolactones

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