NAKAMURA CINTHIA (BR)
DELGADO PAULA (BR)
HOELSCHER FERNANDA (BR)
WO1998047860A1 | 1998-10-29 | |||
WO2018081221A1 | 2018-05-03 | |||
WO1998047860A1 | 1998-10-29 |
US5973203A | 1999-10-26 | |||
EP2818155A1 | 2014-12-31 | |||
JPH05153985A | 1993-06-22 | |||
US20140050687A1 | 2014-02-20 |
CLAIMS 1. A method for preparing at least one fatt y amidoalkyldialkylamine by reacting at least one fat ty acid containing from 8 to 24 carbon atoms with a t least one dialkylaminoalkylamine o f formula (I): in which: R1 represents a divalent alkyl group containing fro m 2 to 6 carbon atoms; R2 and R3 represent, independent ly of each other, monovalent alkyl groups containing from 1 to 4 carbon atoms, using a molar ratio of said dialkylaminoalkylamine to said fatty acid of more than 1 and up to 1.5, in the presence of Candida antarctica lipase as catalyst. 2. The method of claim 1, wherein the fatty acid(s) contain from 10 to 20 carbon atoms, preferably from 12 to 18 carbon atoms. 3. The method of anyone o f the preceding claims, wherein t he fatty acid(s) are chosen from lauric acid, stearic acid, oleic acid, and mixtures thereof, as well as mixtures of fatt y acids compris ing from 8 to 18 carbon atoms and preferably from 12 to 18 carbon atoms. 4. The method o f the preceding claim, wherein the fatty acid(s) are chosen from lauric acid and stearic acid, and preferably lauric acid. 5. The method o f anyone o f the preceding claims, wherein in formula (I) , R1 represents a divalent alkyl group containing 3 or 4 carbon atoms and most preferably 3 carbon atoms. 6. The method o f anyone o f the preceding claims, wherein in formula (I), the R2 and R3 groups are ident ical, and preferably represent methyl or ethyl groups, most preferably R2 and R3 both represent methyl groups. 7. The method of anyone o f the preceding claims, wherein t he dialkylaminoalkylamine of formula (I) is dimethylaminopropyl amine. 8. The method of anyone o f the preceding claims, wherein t he molar rat io of dialkylaminoalkylamine(s) to fat ty acid(s) ranges fro m 1.05 to 1.3, preferably from 1.1 to 1.2. 9. The method of anyone o f the preceding claims, wherein t he catalyst is under t he form o f a so lid catalyst containing Candida Antarctica lipase grafted onto a polymeric support, which is preferably an anionic resin and more preferably an acrylic resin. 10. The method o f anyone o f t he preceding cla ims, wherein Candida Antarctica lipase is present in an amount ranging from 0.2 to 2% by weight, preferably from 0.5 to 1.5% by weight, and most preferably in an amount o f 0.9 to 1.1% by weight, with regard to the total weight of fatty acid(s). 11. The method o f anyone of the preceding claims, wherein the react ion is carried out at a temperature within the range from 75 to 120°C, preferably from 85 to 105°C, and most preferably from 90 to 100°C. 12. The method o f anyone of the preceding claims, wherein the react ion is carried out under vacuum, at a pressure ranging fro m 25.102 to 200.102 Pa, preferably from 50.102 to 100.102 Pa. 13. The method of anyone o f the preceding claims, wherein the react ion is carried out in a batch reactor. 14. The method of the preceding claim wherein after a first react ion cycle the catalyst is recycled to the reactor where it is reused for a next react ion batch. |
EXAMPLES Example 1: Synthesis o f lauramidopropyldimethylamine by react ing lauric acid with dimethylaminopropylamine The syntheses were carried out in a jacketed reactor having a vo lume o f 250 mL coupled with a vacuum pump, a condenser, a mechanic st irrer and a peristalt ic pump for amine feeding. The reactions were performed at 95°C, under vacuum at 50-100 mbar, mechanical agit at ion, and with a fed-batch o f amine. First, the lauric acid was int roduced into the reactor. It can be melted in t he reactor or be melt ed previously to the addit ion. Then, the enzymat ic catalyst was added. The catalyst used was t he commercial product Novozym 435 which contains 21% by weight of Candida Antarctica lipase or iginat ing from Candida Antarctica B , grafted onto an acrylic resin. The amount of enzyme (active matter, ie excluding the support) used corresponds to 1% w/w based on lauric acid. The stoichiometr ic amount of dimethylaminopropylamine (DMAPA) plus 10% of excess was added cont inuously into the reactor for a period of 7 hours. After 7 hours of feeding, the acid index was monitored for each hour. When it became constant, amine excess was added, divided into portions of 1%. For the fir st react ion batch, a rate of 99.5% of conversion was achieved with 11% (molar) o f amine excess. The total react ion t ime was around 15 hours. After the reaction, the agita t ion was turned o ff for the enzymat ic catalyst to go to the bottom of the reactor. The product was removed from the top. Acid index and residual amine were measured to cert ify that all specificat ions were achieved. After removal o f the product (end o f cycle 1), a new reaction cycle was performed using the catalyst remaining in the reactor: a new charge o f lauric acid was added, and the feeding o f dimethylaminopropylamine was started. Three successive reaction cycles were achieved using the same load of catalyst . The table hereunder summarizes the condit ions and results o f the react ion for the three successive cycles. ( contains 21% by weight of Candida Antarctica lipase Example 2: Synthesis o f stearamidopropyldimethylamine by react ing stearic acid with dimethylaminopropylamine The synthesis was carried out in a jacketed reactor having a vo lume o f 250 mL coupled with a vacuum pump, a condenser, a mechanic st irrer and a peristalt ic pump for amine feeding. The reaction was performed at 95°C, under vacuum at 50-100 mbar, mechanical agit at ion, and with a fed-batch o f amine. First, the stearic acid was int roduced into the reactor. It can be melt ed in the reactor or be melt ed previously to the addit ion. Then, the enzymat ic catalyst was added. The catalyst used was t he commercial product Novozym 435 which contains 21% by weight of Candida Antarctica lipase or iginat ing from Candida Antarctica B , grafted onto an acrylic resin. The amount of enzyme (active matter, ie excluding the support) used corresponds to 1% w/w based on lauric acid. The stoichiometric amount of dimethylaminopropylamine (DMAPA) plus 10% of excess was added cont inuously into the reactor for a period of 7 hours. After 7 hours of feeding, the acid index was monitored for each hour. When it became constant, amine excess was added, divided into portions of 1%. A rate of 99.2% of conversion was achieved with 18% (molar) of amine excess. The total react ion time was around 20 hours. After the reaction, the agita t ion was turned o ff for the enzymat ic catalyst to go to the bottom of the reactor. The product was removed from the top. Acid index and residual amine are measured to cert ify that all specificat ions were achieved. The table hereunder summarizes the condit ions and results o f the react ion for the synthesis.
( *) contains 21% by weight of Candida Antarctica lipase The examples above show that the method of t he invent io n provides an efficient route for the synthesis o f fatt y amidoalkyldialkylamines. The benefits o f the enzymat ic process of the invent ion in particular versus chemical synthesis are the reduction o f dialkylaminoalkylamine raw material from 30 to 10-13% and the reduct ion o f the temperature. Both parameters have a significant impact on the process costs. Furthermore in the chemical synthesis, after specifying acidity content, another step is required in order to remove residues o f DMAPA, which is not needed in the method of the invent ion.