Abstract
The amidation reaction based on catalytic coupling of alcohols with amines previously reported by us, using the pincer complexes 1 and 2 as catalysts, was applied to the generation of polyamides from nonactivated diols and diamines. A range of polymers was prepared, with M n up to 26.9 kDa. Unlike the traditional syntheses of polyamides based on carboxylic acid derivatives, which require the use of toxic reagents and generate stoichiometric amounts of waste, this process generates only molecular hydrogen as byproduct. Both aromatic and aliphatic diols and diamines were used. Gel permeation chromatography measurements of the dimethylformamide-soluble polymers and thermal studies of the polyamides were performed. Matrix assisted laser desorption/ionization time-of-flight (MALDI-TOF) spectra are also reported. Thermogravimetric analyses studies indicate that the aromatic polyamides (with the exception of the pyridine-based polyamide) are more thermally stable than the aliphatic ones. This general, environmentally benign method for the synthesis of polyamides is homogeneously catalyzed under neutral conditions by dearomatized ruthenium-pincer complexes 1 and 2 and proceeds in 1,4-dioxane under an inert atmosphere. Conditions for polyamidation in the absence of solvent are also reported, using the pincer complex 2 as catalyst.
| Original language | English |
|---|---|
| Pages (from-to) | 1755-1765 |
| Number of pages | 11 |
| Journal | Journal of Polymer Science, Part A: Polymer Chemistry |
| Volume | 50 |
| Issue number | 9 |
| DOIs | |
| Publication status | Published - May 1 2012 |
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Keywords
- alcohol dehydrogenation
- amidation
- catalysis
- catalysts
- dihydrogen
- homogeneous catalysis
- pincer
- pincer complex
- polyamides
- ruthenium complex
ASJC Scopus subject areas
- Materials Chemistry
- Polymers and Plastics
- Organic Chemistry
Cite this
Synthesis of polyamides from diols and diamines with liberation of H 2 . / Gnanaprakasam, Boopathy; Balaraman, Ekambaram; Gunanathan, Chidambaram; Milstein, David.
In: Journal of Polymer Science, Part A: Polymer Chemistry, Vol. 50, No. 9, 01.05.2012, p. 1755-1765.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Synthesis of polyamides from diols and diamines with liberation of H 2
AU - Gnanaprakasam, Boopathy
AU - Balaraman, Ekambaram
AU - Gunanathan, Chidambaram
AU - Milstein, David
PY - 2012/5/1
Y1 - 2012/5/1
N2 - The amidation reaction based on catalytic coupling of alcohols with amines previously reported by us, using the pincer complexes 1 and 2 as catalysts, was applied to the generation of polyamides from nonactivated diols and diamines. A range of polymers was prepared, with M n up to 26.9 kDa. Unlike the traditional syntheses of polyamides based on carboxylic acid derivatives, which require the use of toxic reagents and generate stoichiometric amounts of waste, this process generates only molecular hydrogen as byproduct. Both aromatic and aliphatic diols and diamines were used. Gel permeation chromatography measurements of the dimethylformamide-soluble polymers and thermal studies of the polyamides were performed. Matrix assisted laser desorption/ionization time-of-flight (MALDI-TOF) spectra are also reported. Thermogravimetric analyses studies indicate that the aromatic polyamides (with the exception of the pyridine-based polyamide) are more thermally stable than the aliphatic ones. This general, environmentally benign method for the synthesis of polyamides is homogeneously catalyzed under neutral conditions by dearomatized ruthenium-pincer complexes 1 and 2 and proceeds in 1,4-dioxane under an inert atmosphere. Conditions for polyamidation in the absence of solvent are also reported, using the pincer complex 2 as catalyst.
AB - The amidation reaction based on catalytic coupling of alcohols with amines previously reported by us, using the pincer complexes 1 and 2 as catalysts, was applied to the generation of polyamides from nonactivated diols and diamines. A range of polymers was prepared, with M n up to 26.9 kDa. Unlike the traditional syntheses of polyamides based on carboxylic acid derivatives, which require the use of toxic reagents and generate stoichiometric amounts of waste, this process generates only molecular hydrogen as byproduct. Both aromatic and aliphatic diols and diamines were used. Gel permeation chromatography measurements of the dimethylformamide-soluble polymers and thermal studies of the polyamides were performed. Matrix assisted laser desorption/ionization time-of-flight (MALDI-TOF) spectra are also reported. Thermogravimetric analyses studies indicate that the aromatic polyamides (with the exception of the pyridine-based polyamide) are more thermally stable than the aliphatic ones. This general, environmentally benign method for the synthesis of polyamides is homogeneously catalyzed under neutral conditions by dearomatized ruthenium-pincer complexes 1 and 2 and proceeds in 1,4-dioxane under an inert atmosphere. Conditions for polyamidation in the absence of solvent are also reported, using the pincer complex 2 as catalyst.
KW - alcohol dehydrogenation
KW - amidation
KW - catalysis
KW - catalysts
KW - dihydrogen
KW - homogeneous catalysis
KW - pincer
KW - pincer complex
KW - polyamides
KW - ruthenium complex
UR - http://www.scopus.com/inward/record.url?scp=84859135605&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84859135605&partnerID=8YFLogxK
U2 - 10.1002/pola.25943
DO - 10.1002/pola.25943
M3 - Article
AN - SCOPUS:84859135605
VL - 50
SP - 1755
EP - 1765
JO - Journal of Polymer Science, Part A: Polymer Chemistry
JF - Journal of Polymer Science, Part A: Polymer Chemistry
SN - 0887-624X
IS - 9
ER -