The Catalytic Effects of 1,4-Diaza[2.2.2]bicycloöctane for Isocyanate Reactions

Farkas, A.; Flynn, Kenneth G.

doi:10.1021/ja01488a036

Cited by 64 publications

(23 citation statements)

References 1 publication

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“…The reaction between HDI and DEG did not proceed without a catalyst, but when the Mt(acac) n complex was used as catalyst, the reaction between HDI and DEG proceeded speedily. The Mn(acac) 2 catalyst reached a high conversion (> 80%) after 60 min and attained total conversion after 120 min, whereas Fe(acac) 3 showed 85% conversion after 120 min Fe(acac) 3 catalyst has good to excellent catalytic activity for the reaction between HDI and ethanol. 14,15 However, under our experimental conditions, the catalytic activity of Mn(acac) 2 was even higher, and the catalytic activity of Mn(acac) 2 was about twice that of Fe(acac) 3 .…”

Section: Resultsmentioning

confidence: 97%

“…102.2 2.8 TEDA-Fe(acac) 3 49.3 1.3 TEDA-Co(acac) 2 14.4 0.4 TEDA-Ni(acac) 2 1.6 -TEDA-Cu(acac) 2 3.5…”

Section: Reaction Between Hdi and Deg Catalyzed By Metal-β-diketonementioning

confidence: 99%

“…However, the reaction rate of aliphatic isocyanates on preparations of polyurethane is very slow compared with aromatic isocyanates. Therefore, tertiary amines [1][2][3][4][5] and tin compounds, [6][7][8][9][10] having excellent catalytic activity, are used mainly as catalysts for polyurethane formation. In particular, dibutyltin dilaurate (DBTDL) has been used.…”

mentioning

confidence: 99%

“…Recently, late transition metal complexes such as metal-β-diketone complexes (Mt(acac) n ) are being researched with great interest. [11][12][13] For example, Fe(acac) 3 and Cu(acac) 2 complexes are used for the reaction between hexamethylene diisocyante (HDI) and alcohols. 14,15 Although there is sufficiently the catalytic activity for only Mt(acac) n complexes, the increase of the catalytic activity is expected by the cocatalyst.…”

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confidence: 99%

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Amine-Manganese Complex as an Efficient Catalyst for Polyurethane Syntheses

Inoue

Nagai

Okamoto

2002

Polym J

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Section: Resultsmentioning

confidence: 97%

“…102.2 2.8 TEDA-Fe(acac) 3 49.3 1.3 TEDA-Co(acac) 2 14.4 0.4 TEDA-Ni(acac) 2 1.6 -TEDA-Cu(acac) 2 3.5…”

Section: Reaction Between Hdi and Deg Catalyzed By Metal-β-diketonementioning

confidence: 99%

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confidence: 99%

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confidence: 99%

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Amine-Manganese Complex as an Efficient Catalyst for Polyurethane Syntheses

Inoue

Nagai

Okamoto

2002

Polym J

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“…In order to solve this problem, aliphatic isocyanates, which are resistant to coloring by air and light, are used. However, it is already clear that aliphatic isocyanates are less reactive than aromatic isocyanates and they are not able to use conventional catalysts such as tertiary amines [1][2][3][4][5] in the reaction between aliphatic isocyanates and alcohols. Although dibutyltin dilaurate (DBTDL) is generally used as a catalyst, [6][7][8] this compound contains a little tributyltin which is notable for environmental contamination.…”

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confidence: 99%

Efficient Cobalt Complex on the Reaction between Isophorone Diisocyanate and Diethylene Glycol

Inoue

Nagai

2005

Polym J

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Polyurethane is widely used for new industrial materials. However, there is the problem of polyurethane prepared from aromatic isocyanates being colored by air and light. In order to solve this problem, aliphatic isocyanates, which are resistant to coloring by air and light, are used. However, it is already clear that aliphatic isocyanates are less reactive than aromatic isocyanates and they are not able to use conventional catalysts such as tertiary amines [1][2][3][4][5] in the reaction between aliphatic isocyanates and alcohols. Although dibutyltin dilaurate (DBTDL) is generally used as a catalyst, 6-8 this compound contains a little tributyltin which is notable for environmental contamination. Accordingly, it is unfavorable to use it as catalyst. Thus, the development of a new catalyst having a high catalytic activity is necessary. 9 Recently, a new group (or type) of catalysts, late transition metal complexes, are being researched with great interest as catalysts. 10,11 In particular, metal--diketone complexes (Mt(acac) n ) are gaining much attention. For example, Fe(acac) 3 and Cu(acac) 2 complexes are used in the reaction between hexamethylene diisocyanate (HDI) and alcohols. 12,13 We have also already reported that Mt(acac) n and tertiary amine-Mt(acac) n complexes had adjective catalytic activity on the reaction between HDI and diethylene glycol (DEG). 14 In the present paper, the catalytic activities and kinetics of Mt(acac) n and Co(f 6 acac) 2 -Co(acac) 2 complexes, on the reaction between isophorone diisocyanate (IPDI) and DEG are described. The resulting data clearly shows that the catalytic activity of Co(f 6 acac) 2 -Co(acac) 2 complex is the very highest on the reaction between IPDI and DEG. EXPERIMENTAL MaterialsIsophorone diisocyanate (IPDI, Nacalai Tesque Inc.) and diethylene glycol (DEG, Nacalai Tesque Inc.) were distilled immediately under reduced pressure (1 mmHg) before use. Manganese(II) (Mn(acac) 2 ) and iron(III) acethylacetonates (Fe(acac) 3 ) were obtained from Nacalai Tesque Inc. Cobalt(II) (Co-(acac) 2 ), nickel(II) (Ni(acac) 2 ), and copper(II) acethylacetonates (Cu(acac) 2 ), cobalt(II) hexafluoroacethylacetonate (Co(f 6 acac) 2 ) and dibutyltin dilaurate (DBTDL) were obtained from Tokyo Kasei Kogyo Co., Ltd. and used without further purification. Toluene (Nacalai Tesque Inc.) and N,N-dimethylformamide (DMF, Nacalai Tesque Inc.) were dehydrated over a molecular sieve (4 A). Other reagents are commercially available and were used as received.Reaction Catalyzed by Co(f 6 acac) 2 -Co(acac) 2 Complex between Isophorone Diisocyanate and Diethylene Glycol A DMF solution containing a catalyst and a isocyanate was prepared from Co(acac) 2 (0.0798 g, 0.31 mmol), Co(f 6 acac) 2 (0.0376 g, 0.08 mmol), IPDI (1.38 g, 6.20 mmol) and DMF (15 mL), and this DMF solution was degassed under an argon atmosphere. DEG (0.66 g, 6.20 mmol) and DMF (70 mL) solutions were placed in a 200 mL three-necked round bottom flask fitted with a mixer and an argon inlet tube, and then the resulting solution was sti...

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Synthese von Pfropfcopolymeren des Polyacrylnitrils mit Polyethylenoxid

Šalabi¹,

Gabrieljan²,

Rogovin³

1979

Acta Polymerica

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Durch Umsetzung eines carboxylgruppenhaltigen Acrylnitricopolymers mit einem Isocyanatendgruppen enthaltenden Polyethylenoxid der relativen Molekülmasse 1000 wurden in DMF‐Lösung entsprechende Pfropfcopolymere erhalten. Die Abhängigkeit der Pfropfcopolymerausbeute von der chemischen Zusammensetzung des Oligomers, der Konzentration des Makrodiisocyanates in der Lösung, der Reaktionszeit, der Temperatur sowie der Konzentration des Katalysators und des Ausgangscopolymers in der Lösung wurde untersucht. Es wird ein Reaktionsmechanismus vorgeschlagen, die Aktivierungsenergie der Pfropfreaktion wurde zu 11,6 kcal/mol ermittelt. Die Pfropfcopolymere zeichnen sich durch sehr hohe spezifische Viskositätswerte und eine niedrige Viskosität der äquikonzentrierten Lösungen gegenüber den Lösungen des Ausgangscopolymers aus.

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The Catalytic Effects of 1,4-Diaza[2.2.2]bicycloöctane for Isocyanate Reactions

Cited by 64 publications

References 1 publication

Amine-Manganese Complex as an Efficient Catalyst for Polyurethane Syntheses

Amine-Manganese Complex as an Efficient Catalyst for Polyurethane Syntheses

Efficient Cobalt Complex on the Reaction between Isophorone Diisocyanate and Diethylene Glycol

Synthese von Pfropfcopolymeren des Polyacrylnitrils mit Polyethylenoxid

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