Method for preparing curable amide gellant compounds
View Patent ↗Disclosed is a process for preparing a compound of the formula wherein R 1 is an alkyl group having at least one ethylenic unsaturation, an arylalkyl group having at least one ethylenic unsaturation, or an alkylaryl group having at least one ethylenic unsaturation, R 2 and R 3 each, independently of the others, are alkylene groups, arylene groups, arylalkylene groups, or alkylarylene groups, and n is an integer representing the number of repeat amide units and is at least 1, said process comprising: (a) reacting a diacid of the formula HOOC—R 2 —COOH with a diamine of the formula in the absence of a solvent while removing water from the reaction mixture to form an acid-terminated oligoamide intermediate; and (b) reacting the acid-terminated oligoamide intermediate with a monoalcohol of the formula R 1 —OH in the presence of a coupling agent and a catalyst to form the product.
1. A process for preparing a compound of the formula
wherein R 1 is (i) an alkyl group having at least one ethylenic unsaturation therein, including linear and branched, cyclic and acyclic, and substituted and unsubstituted alkyl groups, and wherein hetero atoms either may or may not be present in the alkyl group, (ii) an arylalkyl group having at least one ethylenic unsaturation therein, including substituted and unsubstituted arylalkyl groups, wherein the alkyl portion of the arylalkyl group can be linear or branched, cyclic or acyclic, and substituted or unsubstituted, and wherein hetero atoms either may or may not be present in either the aryl or the alkyl portion of the arylalkyl group, or (iii) an alkylaryl group having at least one ethylenic unsaturation therein, including substituted and unsubstituted alkylaryl groups, wherein the alkyl portion of the alkylaryl group can be linear or branched, cyclic or acyclic, and substituted or unsubstituted, and wherein hetero atoms either may or may not be present in either the aryl or the alkyl portion of the alkylaryl group, R 2 and R 3 each, independently of the others, are (i) alkylene groups, including linear and branched, saturated and unsaturated, cyclic and acyclic, and substituted and unsubstituted alkylene groups, and wherein hetero atoms either may or may not be present in the alkylene group, (ii) arylene groups, including substituted and unsubstituted arylene groups, and wherein hetero atoms either may or may not be present in the arylene group, (iii) arylalkylene groups, including substituted and unsubstituted arylalkylene groups, wherein the alkyl portion of the arylalkylene group can be linear or branched, saturated or unsaturated, cyclic or acyclic, and substituted or unsubstituted, and wherein hetero atoms either may or may not be present in either the aryl or the alkyl portion of the arylalkylene group, or (iv) alkylarylene groups, including substituted and unsubstituted alkylarylene groups, wherein the alkyl portion of the alkylarylene group can be linear or branched, saturated or unsaturated, cyclic or acyclic, and substituted or unsubstituted, and wherein hetero atoms either may or may not be present in either the aryl or the alkyl portion of the alkylarylene group, and n is an integer representing the number of repeat amide units and is at least 1, said process comprising: (a) reacting a diacid of the formula
HOOC—R 2 —COOH
with a diamine of the formula
in the absence of a solvent while removing water from the reaction mixture to form an acid-terminated oligoamide intermediate of the formula
and (b) reacting the acid-terminated oligoamide intermediate with a monoalcohol of the formula
R 1 —OH
in the presence of a coupling agent and a catalyst to form the product of the formula
2. A process according to claim 1 wherein about n+1 molar equivalents of the diacid and from about 0.75 n to about 1.5 n molar equivalents of the diamine are reacted to form the oligoamide intermediate.
3. A process according to claim 1 wherein the reaction between the diacid and the diamine to form the oligoamide intermediate is carried out at a temperature of at least about 130° C., and wherein the reaction between the diacid and the diamine to form the oligoamide intermediate is carried out at a temperature of no more than about 180° C.
4. A process according to claim 1 wherein the reaction between the diacid and the diamine to form the oligoamide intermediate is carried out for at least about 2 hours.
5. A process according to claim 1 wherein the coupling agent is 1,3-dicyclohexylcarbodiimide, 1-[3-(dimethylamino)propyl]3-ethylcarbodiimide HCl, N,N-carbonyldiimidazole, N-cyclohexyl-N′-(2-morpholinoethyl)-carbodiimide methyl-p-toluenesulfonate, (benzotriazol-1-yloxy)tris(dimethylamino)phosphonium hexafluorophosphate, (o-benzotriazol-1-yl)-N,N,N′,N′-bis(tetramethylene)uronium hexafluorophosphate, bis(2-oxo-3-oxazolidinyl)phosphonic chloride, (1H-1,2,3-benzotriazol-1-yloxy)tris(pyrrolidino)phosphonium hexafluorophosphate, or mixtures thereof.
6. A process according to claim 1 wherein the catalyst is 4-dimethylaminopyridine, triethylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene, or mixtures thereof.
7. A process according to claim 1 wherein the oligoamide intermediate and the monoalcohol are present in relative amounts of at least about 2 moles of monoalcohol per every 1 mole of oligoamide intermediate.
8. A process according to claim 1 wherein the oligoamide intermediate and the coupling agent are present in relative amounts of at least about 1.8 moles of coupling agent per every 1 mole of oligoamide intermediate.
9. A process according to claim 1 wherein the oligoamide intermediate and the catalyst are present in relative amounts of at least about 0.05 mole of catalyst per every 1 mole of oligoamide intermediate.
10. A process according to claim 1 wherein the reaction between the oligoamide intermediate and the monoalcohol is carried out at a temperature of at least about 15° C., and wherein the reaction between the oligoamide intermediate and the monoalcohol is carried out at a temperature of no more than about 50° C.
11. A process according to claim 1 wherein the reaction between the oligoamide intermediate and the monoalcohol is carried out for a period of at least about 2.5 hours.
12. A process according to claim 1 wherein R 1 is an alkyl group having at least one ethylenic unsaturation therein, including linear and branched, cyclic and acyclic, and substituted and unsubstituted alkyl groups, and wherein hetero atoms either may or may not be present in the alkyl group.
13. A process according to claim 12 wherein the alkyl group is an unsubstituted alkyl group.
14. A process according to claim 1 wherein R 1 is of the formula
wherein m is an integer representing the number of repeating [O—(CH 2 ) 2 ] units.
15. A process according to claim 1 wherein R 2 is an alkylene group, including linear and branched, saturated and unsaturated, cyclic and acyclic, and substituted and unsubstituted alkylene groups, and wherein hetero atoms either may or may not be present in the alkylene group.
16. A process according to claim 15 wherein the alkylene group is a saturated unsubstituted alkylene group.
17. A process according to claim 1 wherein R 2 is an alkylene group of the formula —C 34 H 56+a — and are branched alkylene groups which may include unsaturations and cyclic groups, wherein a is an integer of 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 1, or 12.
18. A process according to claim 17 wherein R 2 includes isomers of the formula
19. A process according to claim 1 wherein R 3 is an alkylene group, including linear and branched, saturated and unsaturated, cyclic and acyclic, and substituted and unsubstituted alkylene groups, and wherein hetero atoms either may or may not be present in the alkylene group.
20. A process according to claim 19 wherein the alkylene group is a saturated unsubstituted alkylene group.
21. A process according to claim 1 wherein R 3 is a —CH 2 CH 2 — group.
22. A process according to claim 1 wherein n is no more than about 20.
23. A process according to claim 1 wherein n is 1 or 2.
24. A process according to claim 1 wherein the compound is of the formula
wherein —C 34 H 56+a — represents a branched alkylene group which may include unsaturations and cyclic groups, wherein a is an integer of 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 and wherein n is 1 or 2.
25. A process according to claim 1 wherein the compound is of the formula
26. A process according to claim 1 wherein the compound is of the formula
or mixtures thereof, wherein —C 34 H 56+a — represents a branched alkylene group which may include unsaturations and cyclic groups, wherein a is an integer of 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12, n is 1 or 2, and m is an integer representing the number of repeating [O—(CH 2 ) 2 ] units.
27. A process according to claim 1 wherein the compound is of the formula
or mixtures thereof, wherein n is 1 or 2 and m is an integer representing the number of repeating [O—(CH 2 ) 2 ] units.