Organic oligomers of acylglycerol

Abstract

Organic oligomers of acylglycerol having general formula (I): Formula (I), in which M1 and Q1 are organic groups; G11 is a hydroxylpropyl group; G12 and G13 are ?/?-acylglycerols; n is a natural integer from the range [0; 8]; m is a natural integer from the range [0; 4]; and p is a natural integer from the range [0; 3].

Claims

1. An acylated organic glycerol oligomer of general formula (I): ##STR00024## wherein: M.sub.1 is an organic group selected from formulae (I.sub.A), (I.sub.B), (I.sub.C), and (I.sub.D): ##STR00025## wherein R is a hydrocarbon group, a saturated hydrocarbon group, an unsaturated hydrocarbon group or a branched hydrocarbon group, having from 1 to 21 carbon atoms; G.sub.11 is selected from the of hydroxylated propyl groups of formulae (II.sub.A) and (II.sub.B): ##STR00026## G.sub.12 and G.sub.13 are ?/?-hydroxyacylated propyl groups of formula (III): ##STR00027## and Q.sub.1 is chosen from the group formed of hydrogen and organic groups formed of at least two atoms bonded by covalent bonds and belonging to the group formed of carbon (C), hydrogen (H) and oxygen (O); n is a natural integer less than 9 such that if n=0, then M.sub.1 is of formula (I.sub.C) or (I.sub.D); and m is a non-zero integer less than 5; and p is an integer less than 4.

2. The oligomer as claimed in claim 1, wherein Q.sub.1 is selected from the group consisting of: hydrogen (H), hydroxylated propyl groups of formula (III.sub.A): ##STR00028## hydroxylated propyl groups of formula (III.sub.B): ##STR00029## and groups of formulae (I.sub.A), (I.sub.B), (I.sub.C) and (I.sub.D).

3. An acylated organic glycerol oligomer of formula (IV): ##STR00030## wherein R is a hydrocarbon group, a saturated hydrocarbon group, an unsaturated hydrocarbon group or a branched hydrocarbon group, having from 1 to 21 carbon atoms; and a is a non-zero integer less than 9.

4. An acylated organic glycerol oligomer of formula (V): ##STR00031## wherein R is a hydrocarbon group, a saturated hydrocarbon group, an unsaturated hydrocarbon group or a branched hydrocarbon group, having from 1 to 21 carbon atoms; and a is a non-zero integer less than 9.

5. An acylated organic glycerol oligomer of formula (VI): ##STR00032## wherein R is a hydrocarbon group, a saturated hydrocarbon group, an unsaturated hydrocarbon group or a branched hydrocarbon group, having from 1 to 21 carbon atoms; and a is a non-zero integer less than 4.

6. The oligomer claim 1, having the formula (VII): ##STR00033## wherein b is a non-zero integer less than 5.

7. The oligomer of claim 1, having the formula (VIII): ##STR00034## wherein b is a non-zero integer less than 5.

8. The oligomer of claim 1, having the formula (IX): ##STR00035## wherein b is a non-zero integer less than 5.

9. The oligomer of claim 1, having the formula (X): ##STR00036## wherein b is a non-zero integer less than 5.

10. The oligomer of claim 1, having the formula (XI): ##STR00037## wherein b is a non-zero integer less than 5.

11. The oligomer of claim 1, having the formula (XII): ##STR00038## wherein b is a non-zero integer less than 5.

12. The oligomer of claim 1, having the formula (XIII): ##STR00039## wherein b is a non-zero integer less than 5.

13. The oligomer of claim 1, having the formula (XIV): ##STR00040## wherein b is a non-zero integer less than 5.

14. The oligomer of claim 1, wherein R is a hydrocarbon group selected from the group consisting of: saturated hydrocarbon groups of the general formula C.sub.qH.sub.2q+1 wherein q is an integer from 1 to 21; and unsaturated hydrocarbon groups, monounsaturated hydrocarbon groups of the general formula C.sub.sH.sub.2s-1 wherein s is an integer from 1 to 21, and polyunsaturated hydrocarbon groups.

15. The oligomer of claim 1, wherein R is a hydrocarbon group selected from the group consisting of methyl (CH.sub.3), ethyl (CH.sub.2CH.sub.3), n-propyl (CH.sub.2CH.sub.2CH.sub.3), iso-propyl (CH(CH.sub.3).sub.2), n-butyl (CH.sub.2CH.sub.2CH.sub.2CH.sub.3), iso-butyl (CH.sub.2CH(CH.sub.3).sub.2), tert-butyl (C(CH.sub.3).sub.3), n-pentyl (CH.sub.2(CH.sub.2).sub.3CH.sub.3), hexyl ((CH.sub.2).sub.5CH.sub.3) octyl ((CH.sub.2).sub.7CH.sub.3) undecyl ((CH.sub.2).sub.10CH.sub.3), pentadecyl ((CH.sub.2).sub.14CH.sub.3) heptadecyl ((CH.sub.2).sub.16CH.sub.3), 9-ene-decyl (CH?CH(CH.sub.2).sub.7CH.sub.3) and 9-ene-heptadecyl ((CH.sub.2).sub.7CH?CH(CH.sub.2).sub.7CH.sub.3).

16. A liquid organic composition comprising at least one acylated organic glycerol oligomer of claim 1.

17. The composition of claim 16, comprising a plurality of said acylated organic glycerol oligomers.

18. The oligomer of claim 2, wherein R is a hydrocarbon group selected from the group consisting of methyl (CH.sub.3), ethyl (CH.sub.2CH.sub.3), n-propyl (CH.sub.2CH.sub.2CH.sub.3), iso-propyl (CH(CH.sub.3).sub.2), n-butyl (CH.sub.2CH.sub.2CH.sub.2CH.sub.3), iso-butyl (CH.sub.2CH(CH.sub.3).sub.2), tert-butyl (C(CH.sub.3).sub.3), n-pentyl (CH.sub.2(CH.sub.2).sub.3CH.sub.3), hexyl ((CH.sub.2).sub.5CH.sub.3), octyl ((CH.sub.2).sub.7CH.sub.3), undecyl ((CH.sub.2).sub.10CH.sub.3), pentadecyl ((CH.sub.2).sub.14CH.sub.3), heptadecyl ((CH.sub.2).sub.16CH.sub.3), 9-ene-decyl (CH?CH(CH.sub.2).sub.7CH.sub.3) and 9-ene-heptadecyl ((CH.sub.2).sub.7CH?CH(CH.sub.2).sub.7CH.sub.3).

19. The oligomer of claim 2, having the following general formula (VII): ##STR00041## wherein b is a non-zero integer less than 5.

Description

EXAMPLE 1

Synthesis of (Cyclic) ?/?-Acylated Glycerol Carbonic Esters as Precursor

(1) The synthesis of (cyclic) ?/?-acylated glycerol carbonic esters, in particular of ?/?-heptanoic glycerol carbonic ester (ECG-C7), a/a-nonanoic glycerol carbonic ester (ECG-C9), ?/?-undecylenoic glycerol carbonic ester (ECG-C11:1) and ?/?-oleic glycerol carbonic ester (ECG-C18:1), is carried out by esterification of the cyclic ?/?-hydroxylated glycerol carbonate with the corresponding fatty acid.

(2) 1.64 mol of fatty acid and 0.0078 mol of 4-methylbenzenesulfonic acid (CAS no. 6192-52-5, para-toluenesulfonic acid, ApTs) are placed in a 500 ml reactor equipped with a mechanical stirring device, a device for placing under reduced pressure and a Dean-Stark device for removing the water that forms. The temperature of the mixture is brought to a temperature of 110? C. under reduced pressure of 800 hPa for a period of 15 minutes. 0.84 mol of (cyclic) ?/?-hydroxylated glycerol carbonate is then added dropwise to the reactor with mechanical stirring at 800 revolutions per minute (rpm) over a period of 15 minutes. The reactor is placed in an oil bath brought to a temperature of 110? C. with mechanical stirring (800 rpm) for 3 hours.

EXAMPLE 2

Purification of the (Cyclic) ?/?-Acylated Glycerol Carbonic Esters

(3) The reaction mixture is diluted in 150 ml of ethyl ether, and the mixture obtained is placed in a 1 liter separating funnel. The mixture is washed in succession with 4 volumes of water saturated with NaCl until the aqueous phase is neutral. The washed organic phase is dried over magnesium sulfate and then separated from the hydrated magnesium sulfate by filtration. The ether of the organic phase is removed by evaporation under reduced pressure. A mass of dry product of 277 g is obtained. The (cyclic) ?/?-acylated glycerol carbonic ester is separated from the excess fatty acids by thin film distillation under reduced pressure (0.6 hPa) at a temperature that is below the boiling point of the fatty acid under that reduced pressure and below 155? C. The (cyclic) ?/?-acylated glycerol carbonic ester is obtained, the purity of which, evaluated by gas phase chromatography, is from 85% to 95%.

EXAMPLE 3

Synthesis of the Cyclic ?/?-Acetylated Glycerol Carbonic Ester (ECG-C2)

(4) 472 g of cyclic glycerol carbonate (4-(hydroxymethyl)-1,3-dioxolan-2-one, CAS 931-40-8) and 4 g of Lewatit K2431 resin are placed in a 2-liter three-necked glass flask equipped with a mechanical stirrer and with a coolant and placed in an oil bath. 6 mol of acetic anhydride are added dropwise to the reactor in such a manner as to control and maintain the temperature of the reactor at 50? C., with mechanical stirring at 800 rpm for 4 hours.

(5) The excess acetic anhydride is removed by evaporation at a temperature of 60? C. and under reduced pressure of 55 hPa. The linear ?/?-acetylated glycerol carbonic ester is purified by the thin film technique carried out in an evaporator/separator at a temperature of 170? C. and under reduced pressure of 0.33 hPa. The ?/?-acetylated glycerol carbonic ester is obtained, the purity of which, evaluated by gas phase chromatography, is from 98% to 99%.

(6) The structural characteristics of the (cyclic) ?/?-acylated glycerol carbonic esters obtained in Examples 1, 2 and 3 are given in Table 1 below.

(7) TABLE-US-00001 TABLE 1 Mass spectrometry, Purity, % .sup.13C, .sup.1H NMR FTIR m/z ECG-C2 98 conforms conforms 160.1 ECG-C7 94 conforms conforms 230.2 ECG-C9 95 conforms conforms 258.3 ECG-C11:1 85 conforms conforms 284.3 ECG-C18:1 96 conforms conforms 382.5

EXAMPLE 4

Oligomerization of the (Cyclic) ?/?-Acetylated Glycerol Carbonic Ester (ECG-C2)

(8) The oligomerization of the ?/?-acetylated glycerol carbonic ester (ECG-C2) obtained in Example 3 is carried out in the presence of a metal catalyst and of glycerol as organic initiator, under the conditions described in Table 2 below.

(9) TABLE-US-00002 TABLE 2 Number- Metal catalyst average Mass Mass, Initiator molar ECG-C2, g Type mg Glycerol, g Conditions TC, % masses 4.25 Zinc stearate 25 1.5 160? C., P.sub.atm, 59 393, 195, Zn(C.sub.18H.sub.35O.sub.2).sub.2 2 h 64 8.5 Zn(C.sub.18H.sub.35O.sub.2).sub.2 25 1.5 160? C., P.sub.atm, 95 970, 688, 2 h 352, 274, 202, 190 42.5 Zn(C.sub.18H.sub.35O.sub.2).sub.2 250 7.5 160? C., 61 321, 157, 1800 hPa, 91 2 h 21.25 Zn(C.sub.18H.sub.35O.sub.2).sub.2 125 3.75 160? C., P.sub.atm, 84 714, 336, 2 h 206, 139, 92 21.5 Zn(C.sub.18H.sub.35O.sub.2).sub.2 125 3.75 160? C., P.sub.atm, 99.2 405, 253, 2 h 172, 93 21.5 Zn(C.sub.18H.sub.35O.sub.2).sub.2 125 3.75 160? C., P.sub.atm, 98.4 574, 320, 2 h 160, 95 21.5 Zn(C.sub.18H.sub.35O.sub.2).sub.2 125 3.75 160? C., P.sub.atm, 98.4 395, 189, 2 h 140, 92 8.5 ZnSO.sub.4 50 1.75 160? C., 76 420, 173, 3400 hPa, 122, 84, 2 h 36 9 ZnSO.sub.4 50 1.7 160? C., P.sub.atm, 55 431, 160, 30 h 83 21.25 ZnSO.sub.4 125 3.75 160? C., P.sub.atm, 66 389, 159, 2 h 83 21.5 FeSO.sub.4 8H.sub.2O 60 3.75 160? C., P.sub.atm, 40.3 446, 162, 2 h 96 21.5 ZnO 55 3.75 160? C., P.sub.atm, 46 322, 156, 2 h 95 21.5 MnSO.sub.4, 118 3.75 160? C., P.sub.atm, 51 327, 156, 1H.sub.2O 2 h 96 21.5 MnSO.sub.4, 85 3.75 160? C., P.sub.atm, 34 323, 154, 1H.sub.2O 2 h 94 21.5 ZnSO.sub.4, 1H.sub.2O 125 3.75 160? C., P.sub.atm, 36 327, 157, 2 h 94 21.5 CaCO.sub.3 70 3.75 160? C., P.sub.atm, 31 324, 154, 2 h 94 21.5 Na.sub.2CO.sub.3 74 3.75 160? C., P.sub.atm, 98 632, 314, 2 h 192, 137, 99

(10) The value TC (%) indicates the rate of conversion of the starting (cyclic) ?/?-acylated glycerol carbonic ester. The number-average molar mass values are obtained by analysis of the reaction mixture by gel permeation chromatography on a PLgel 3 ?m MIXED-E column. The acylated organic glycerol oligomers are detected at the column outlet by refractometry and the number-average molecular masses are determined by comparison with polystyrene standards.

(11) The syntheses carried out with a zinc metal catalyst (ZnO, Zn(C.sub.18H.sub.35O.sub.2).sub.2 and ZnSO.sub.4) yield a mixture of oligomers of formula (I) wherein M.sub.1 is of formula (I.sub.A), (I.sub.B), (I.sub.C) or (I.sub.D), Q.sub.1 is of formula (I.sub.A), (I.sub.B), (I.sub.C), (I.sub.D), G.sub.11 or H, n is a natural integer of the interval [0; 8], m is a natural integer of the interval [0; 4], p is a natural integer of the interval [0; 3] and R is a methyl radical.

(12) An example of a mass spectrum of a reaction mixture obtained by carrying out a process of oligomerization of the ?/?-acetylated glycerol carbonic ester (ECG-C2) as described in Example 4 is shown in FIG. 1. There are detected signals corresponding to molecular ions and fragments of m/z values of from 180.9 to 761.4 and corresponding to organic glycerol oligomers of the following particular formulae (A), (B), (C) and (D):

(13) ##STR00020##
wherein c can have the value 1, 2 or 4 and d can have the value 1, 2, 3 or 4;

(14) ##STR00021##
wherein b can have the value 1, 2 or 3;

(15) ##STR00022##
wherein a can have the value 1, 2, 3, 4, 5, 6, 7 or 8; and

(16) ##STR00023##
wherein g can have the value 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.

(17) The syntheses carried out with a non-zinc metal catalyst (FeSO.sub.4, MnSO.sub.4, CaCO.sub.3 and Na.sub.2CO.sub.3) yield a mixture of oligomers of formula (I) wherein M.sub.1 is of formula (I.sub.C) or (I.sub.D), Q.sub.1 is of formula (I.sub.C), (I.sub.D), G.sub.11 or H, n is a natural integer of the interval [0; 8], m=0, p is a natural integer of the interval [0; 3] and R is a methyl radical.

EXAMPLE 5

Oligomerization of (Cyclic) ?/?-Acylated Glycerol Carbonic Esters (ECG-C2, ECG-C7, ECG-C9, ECG-C11:1 and ECG-C18:1)

(18) An oligomerization of the (cyclic) ?/?-acylated glycerol carbonic esters is carried out under the conditions described in Table 3 below.

(19) TABLE-US-00003 TABLE 3 Number- Metal catalyst average ECG, Mass, Initiator molar mass Type mg Glycerol, g Conditions TC, % masses ECG-C2, Zn(C.sub.18H.sub.35O.sub.2).sub.2 125 3.75 160? C., P.sub.atm, 98 714, 335 21.25 g 2 h 206, 139, 92 ECG-C2, ZnSO.sub.4 125 3.75 160? C., P.sub.atm, 66 389, 159, 21.25 g 2 h 83 ECG-C7, ZnSO.sub.4 113 2.42 200? C., P.sub.atm, 64 639, 420, 20 g 2 h 252, 96 ECG-C9, ZnSO.sub.4 110 2.15 180? C., P.sub.atm, 88 992, 541, 20 g 2 h 303, 90 ECG- ZnSO.sub.4 86 1.3 190? C., P.sub.atm, 98 7632, C11:1, 2 h 2113, 1084, 10 g 750, 486 ECG- ZnSO.sub.4 50 0.7 200? C., P.sub.atm, 97 3724, C18:1, 2 h 1787, 10 g 1169, 613, 94

(20) Oligomers having an apparent molar mass which can reach 7600 Da are obtained.

(21) The syntheses carried out with a zinc metal catalyst (Zn(C.sub.18H.sub.35O.sub.2).sub.2 and ZnSO.sub.4) yield a mixture of oligomers of formula (I) wherein M.sub.1 is of formula (I.sub.A), (I.sub.B), (I.sub.C) or (I.sub.D), Q.sub.1 is of formula (I.sub.A), (I.sub.B), (I.sub.C), (I.sub.D), G.sub.11 or H, n is a natural integer of the interval [0; 8], m is a natural integer of the interval [0; 4], p is a natural integer of the interval [0; 3] and R is chosen from methyl (CH.sub.3), hexyl ((CH2).sub.5CH.sub.3), octyl ((CH2).sub.7CH.sub.3), 9-ene-decyl (CH?CH(CH2).sub.7CH.sub.3) and 9-ene-heptadecyl ((CH2).sub.7CH?CH(CH2).sub.7CH.sub.3).

(22) The value TC (%) indicates the rate of conversion of the starting (cyclic) ?/?-acylated glycerol carbonic ester. The apparent molar mass values are obtained by analysis of the reaction mixture by gel permeation chromtatography.

(23) It goes without saying that the invention can be the subject of numerous variant embodiments and applications. In particular, the process of synthesis of the linear ?/?-acylated carbonic esters is subject to an infinite number of variants, in particular as regards the reaction temperature, the reaction pressure, the proportion by mass of metal catalyst, of (cyclic) ?/?-acylated glycerol carbonic ester(s) and of organic initiator.

(24) Of course, this description is given only by way of an illustrative example, and the person skilled in the art will be able to provide numerous modifications, variations and applications thereof without departing from the scope of the invention.