Alpha/alpha-prime-alkoxylated glycerol linear carbonic esters

Abstract

Alpha/alpha-prime/alkoxylated glycerol linear carbonic esters have formula (VI): ##STR00001##
where p is an integer higher than 1, x is an integer equaling 0 or 1 with x not always being zero, and M.sub.1 is hydrogen (H). Q.sub.1 can be a hydrocarbon aliphatic group, an amino hydrocarbon group or an oxygenated amino hydrocarbon group. G.sub.1 can be an /-alkoxylated propyl group of general formula (II): ##STR00002##
where R.sub.4, R.sub.5 and R.sub.6 are variously hydrogen (H), an alkyl or an amino-alkyl group having 1 to 5 carbon atoms, or general formula (VII): ##STR00003##
where R7 is a H or a hydrocarbon group having 1 to 6 carbon atoms, and m is an integer between 0 and 10 inclusive, and X is O or NH.

Claims

1. /-alkoxylated linear glycerol cyclic carbonic ester of formula (VI): ##STR00019## where: p is an integer higher than 1 and differing from 1; x is an integer equaling 0 or 1 and possibly varying in formula (VI) in each group of formula (VI-a): ##STR00020## x not always being zero; and: M.sub.1 is hydrogen (H); and Q.sub.1 is an organic group selected from the group consisting of hydrocarbon aliphatic groups, amino hydrocarbon groups and oxygenated amino hydrocarbon groups; and G.sub.1 is an /-alkoxylated propyl group of following general formula (II): ##STR00021## where: R.sub.4, R.sub.5 and R.sub.6 are hydrogen (H), or R.sub.4 and R.sub.5 are hydrogens (H) and R.sub.6 is an alkyl or an amino-alkyl group having 1 to 5 carbon atoms, or R.sub.4, R.sub.5 and R.sub.6 are selected from the group consisting of hydrogen (H) and organic groups of following general formula (VII): ##STR00022## where: R7 is selected from the group consisting of a H and a hydrocarbon group having 1 to 6 carbon atoms; m is an integer between 0 and 10 inclusive; and X is selected from the group consisting of O and NH.

2. The compound according to claim 1 of formula (VIII): ##STR00023## where: q is an integer higher than 1 and differing from 1; and x is an integer equal to 0 or 1 possibly varying in formula (VIII) in each group (VIII-a): ##STR00024## x not always being zero; and M.sub.3 is hydrogen (H) and Q.sub.3 is an organic group selected from the group consisting of hydrocarbon aliphatic groups, amino hydrocarbon groups and oxygenated amino hydrocarbon groups.

3. The compound according to claim 1 of formula (IX): ##STR00025## where: q is an integer higher than 1 and differing from 1; and x is an integer equal to 0 or 1 possibly varying in formula (IX) in each group of formula (IX-a): ##STR00026## x not always being zero; and M.sub.3 is hydrogen (H); and Q.sub.3 is an organic group selected from the group consisting of hydrocarbon aliphatic groups, amino hydrocarbon groups and oxygenated amino hydrocarbon groups.

4. The compound according to claim 1, wherein Q.sub.1 represents the group CH.sub.2CH.sub.2NH.sub.2.

5. The compounds according to claim 2, wherein Q.sub.3 represents the group CH.sub.2CH.sub.2NH.sub.2.

6. The compounds according to claim 3, wherein Q.sub.3 represents the group CH.sub.2CH.sub.2NH.sub.2.

7. The compound according to claim 1 of formula (V): ##STR00027## where n is an integer higher than 1 and differing from 1.

8. The compound according to claim 1, wherein R.sub.4, R.sub.5 and R.sub.6 are selected from the group consisting of hydrogen (H) and organic groups of formula (VII): ##STR00028## where: R7 is selected from the group consisting of a H and a hydrocarbon group having 1 to 6 carbon atoms; m is an integer between 0 and 10 inclusive; and X is selected from the group consisting of O and NH.

9. A composition comprising at least one /-alkoxylated glycerol linear carbonic ester according to claim 1.

Description

EXAMPLES

Example 1Carbonatation of Glycerol -methyl-ether

(1) A 100 ml glass round-bottomed flask is charged with 1 molar equivalent of glycerol -methyl-ether (3-methoxy-1,2-propanediol), CAS 623-39-2) and 3 molar equivalents of dimethyl carbonate (CAS 616-38-6) under mechanical stirring at a speed of 400 rpm and temperature of 75 C. in the presence of 0.03 molar equivalents of potassium carbonate (CAS 584-08-7) as catalyst for 8 hours. The methyl ether of glycerol cyclic carbonate (GCME) is formed with a yield after isolation of 85% compared with the starting glycerol -methyl-ether.

Example 2Carbonatation of Glycerol -ethyl-ether

(2) A 100 mL glass round-bottomed flask is charged with 1 molar equivalent of glycerol -ethyl-ether (3-ethoxy-1,2-propanediol, CAS 1874-62-0) and 3 molar equivalents of dimethyl carbonate (CAS 616-38-6) under mechanical stirring at a speed of 400 rpm and temperature of 75 C. in the presence of 0.03 molar equivalents of potassium carbonate (CAS 584-08-7) as catalyst for 8 hours. The ethyl ether of glycerol cyclic carbonate is formed with a yield of 85% after isolation.

Example 3Glycerol -methylation and Carbonatation

(3) The methyl ether of glycerol cyclic carbonate (GCME) is prepared from glycerol. 1 molar equivalent of glycerol (CAS 56-81-5) and 10 molar equivalents of dimethyl carbonate (CAS 616-38-6) are placed in an autoclave at a temperature of 230 C. for 3 hours in the presence of 2 molar equivalents of neutral alumina (Al.sub.2O.sub.3) under mechanical stirring at 400 rpm. The glycerol cyclic carbonate methyl ether (GCME) is obtained with a yield of 50% determined by gas phase chromatography coupled to a flame ionization detector (GC-FID). The GCME is isolated by distillation under reduced pressure (18 hPa) at a temperature of 115 C.

Example 4-methylation of Glycerol Cyclic Carbonate

(4) Glycerol cyclic carbonate methyl ether (GCME) is prepared from glycerol cyclic carbonate. 1 molar equivalent of glycerol cyclic carbonate (CAS 931-40-8, 4-hydroxymethyl-1,3-dioxolan-2-one or 4-hydroxymethyl-2-oxo-1,3-dioxolane) and 5 molar equivalents of dimethyl carbonate (CAS 616-38-6) are placed in an autoclave at a temperature of 200 C. for 4 hours in the presence of 1 molar equivalent of neutral alumina (Al.sub.2O.sub.3) and under mechanical stirring at 400 rpm. The glycerol cyclic carbonate methyl ether (GCME) is obtained with a yield of 66% determined by analysis of the reaction medium by gas phase chromatography coupled to a flame ionization detector (GC-DIF). The GCME is isolated by distillation under reduced pressure (18 hPa) at a temperature of 115 C.

(5) By way of indication, it is also possible to prepare the glycerol cyclic carbonate according to the method described in document FR 2 733 232 by catalytic trans-carbonatation of glycerol from an organic cyclic carbonate.

Example 5Oligomerization of the Glycerol Cyclic Carbonate Methyl Ether (GCME) in the Presence of Glycerol as Organic Initiator of Oligomerization

(6) A quantity of GCME, a quantity of glycerol as oligomerization initiator and a quantity of zinc sulfate as catalyst are placed in a 250 mL autoclave. Before the reaction the weight proportion of GCME and glycerol is 85:15 and the weight proportion of catalyst is 0.5% relative to the total weight of the reagents. After gas-tight hermetic sealing of the autoclave it is heated to bring the reaction medium to 180 C. At this temperature of 180 C. the reaction medium is placed at atmospheric pressure and this reaction temperature is held for a time of 2 hours under mechanical stirring at 400 rpm.

(7) Under Fourier Transform Infrared spectroscopy (FTIR) of the reaction medium a strong reduction is observed in the intensity of the vibration band corresponding to the vibration frequency of the GCME carbonyl at 1790 cm.sup.1, and the onset of a band corresponding to the vibration frequency of the carbonyl of the linear carbonate at 1750-1730 cm.sup.1.

Example 6Oligomerization of the Glycerol Cyclic Carbonate Methyl Ether (GCME) in the Presence of Glycerol as Oligomerization Initiator

(8) A quantity of CGME, a quantity of glycerol as oligomerization initiator and a quantity of zinc stearate (CAS 557-05-1, zinc bis-octadecanoate) as catalyst are placed in a 250 mL autoclave. Before the reaction the weight proportion of GCME and glycerol is 85:15 and the weight proportion of catalyst is 0.5% relative to the total weight of the reagents. After gas-tight hermetic sealing of the autoclave it is heated to bring the temperature of the reaction medium to 180 C. At this temperature of 180 C. the reaction medium is placed under atmospheric pressure and this reaction temperature is held for a time of 2 hours under mechanical stirring at 400 rpm.

(9) Under .sup.1HNMR analysis at 4.3 ppm and 3.57 ppm the signals are observed corresponding to the glycerol protons at positions 1-3 and 1-4 relative to the carbon of the linear carbonate. Also between 3.2 ppm and 3.5 ppm the signals are observed corresponding to the glycerol protons at positions 1-2 and 1-3 relative to the glycerol ether-oxide group.

(10) The conversion rate of GCME (disappearance of the cyclic carbonate group), the conversion rate of oligomerization initiator (glycerol) and the mean molar mass of the formed oligomer are given in Table 1 below.

(11) TABLE-US-00001 TABLE 1 GCME Initiator Oligomerization conversion conversion Mean molar mass of initiator rate, % rate, % the oligomer, g/mole Glycerol 95.3 88.7 2410

Example 7Oligomerization of Glycerol Cyclic Carbonate Methyl Ether (GCME) in the Presence of Ethanolamine as Oligomerization Initiator

(12) A quantity of GCME, a quantity of ethanolamine (CAS 141-43-5, 2-amino-1-ethanol) as oligomerization initiator and a quantity of zinc stearate (CAS 557-05-1, zinc bis-octadecanoate) are placed in a 250 mL autoclave. Before the reaction the weight proportion of GCME and glycerol is 85:15 and the proportion of catalyst is 0.5% relative to the total weight of the reagents. After gas-tight hermetic sealing of the autoclave, it is heated to bring the temperature of the reaction medium to 180 C. At this temperature of 180 C. the reaction medium is placed under atmospheric pressure and this reaction temperature is held for a time of 2 hours under mechanical stirring at 400 rpm.

(13) The conversion rate of GCME (disappearance of the cyclic carbonate group), the conversion rate of oligomerization initiator (2-amino-1-ethanol) and the mean molar mass of the /-alkoxylated glycerol carbonic ester oligomers obtained are given in Table 2 below:

(14) TABLE-US-00002 TABLE 2 GCME Mean molar mass of the Oligomerization initiator conversion rate, % oligomer, g/mole 2-amino-1-ethanol 100 2460 2-amino-1-ethanol 100 2440

(15) It was found that 16% to 20% of the starting amino ethanolamine groups are contained in the oligomer obtained.

(16) Analysis by Fourier transform infrared spectroscopy of the composition obtained by treating GCME with ethanolamine (EA) shows the complete disappearance of the signal at 1794 cm.sup.1 corresponding to the carbonyl of the GCME precursor and the onset of a signal at 1750 cm.sup.1 corresponding to the linear carbonic ester carbonyl of the oligomer obtained. This analysis did not show any signal at 1710 cm.sup.1 corresponding to the carbonyl of a linear urethane function.

Example 8Oligomerization of a Mixture of GCME and Glycerol Cyclic Carbonate in the Presence of Ethanolamine as Oligomerization Initiator

(17) A quantity of GCME, a quantity of glycerol cyclic carbonate, a quantity of ethanolamine (CAS 141-43-5, 2-amino-1-ethanol) as oligomerization initiator and a quantity of zinc stearate (CAS 557-05-1, zinc octadecanoate) are placed in a 250 mL autoclave. Before the reaction the weight proportion of GCME, of glycerol cyclic carbonate and of ethanolamine is 42.5:42.5:15 and the proportion of catalyst is 0.5% relative to the total weight of the reagents. After gas-tight hermetic sealing of the autoclave it is heated to bring the temperature of the reaction medium to 180 C. At this temperature of 180 C. the reaction medium is placed under atmospheric pressure and this reaction temperature is held for a time of 2 hours under mechanical stirring at 400 rpm.

Example 9Oligomerization of the Glycerol Cyclic Carbonate Methyl Ether (GCME) in the Presence of 3-(2-hydroxyethyl)imidazolidin-2-One (HEI) as Oligomerization Initiator

(18) GCME, HEI as oligomerization initiator and zinc stearate (CAS 557-05-1, zinc octadecanoate) are placed in a 250 mL autoclave. Before the reaction, the weight proportion of CGME and of glycerol is 85:15 and the proportion of catalyst is 0.5% relative to the total weight of the reagents. After gas-tight hermetic sealing of the autoclave it is heated to bring the temperature of the reaction medium to 180 C. At this temperature of 180 C. the reaction medium is placed under atmospheric pressure and this reaction temperature is held for a time of 2 hours under mechanical stirring at 400 rpm.

(19) The conversion rate of GCME (disappearance of the cyclic carbonate group), the conversion rate of the oligomerization initiator (HEI) and the mean molar mass of the oligomer obtained are given in Table 3 below.

(20) TABLE-US-00003 TABLE 3 GCME Initiator Oligomerization conversion conversion Mean molar mass of initiator rate, % rate, % the oligomer, g/mole HEI 75.5 91.1 2460

Example 10Oligomerization of Glycerol Cyclic Carbonate Methyl Ether (GCME) in the Presence of Glycerol

(21) A quantity of CGME, a quantity of glycerol and a quantity of catalyst are placed in a 250 mL autoclave at ambient temperature.

(22) The autoclave is hermetically sealed and the composition is heated to bring its temperature to the reaction temperature. When this reaction temperature is reached, the reactor is placed under atmospheric pressure and the formed composition is held at this reaction temperature under mechanical stirring at 400 rpm.

(23) The reaction temperature, type of catalyst, reaction time, weight ratio of precursor (GCME) and glycerol and the conversion rate of the precursor are given in Table 4 below.

(24) TABLE-US-00004 TABLE 4 Reaction GCME/ Reaction time, Glycerol, Conversion, temperature, C. Catalyst h w/w % 180 Zn stearate 2 20 10 180 Zn stearate 2 10 19 180 Zn stearate 3 5 72 180 Zn stearate 6 5 48.5 180 Zn stearate 3 4.5 77 180 Zn stearate 2 4.5 50 180 Zn stearate 2 4.5 64 180 ZnSO.sub.4 2 5.0 15.5 180 K.sub.2CO.sub.3 2 5.9 100

Example 11Oligomerization of Glycerol Cyclic Carbonate Methyl Ether (GCME) Catalysed by Zinc Stearate in the Presence of an Oligomerization Initiator

(25) At ambient temperature quantity of GCME, quantity of oligomerization initiator selected from among triethanolamine (TEA), ethanolamine (EA), ethane-1,2-diamine (EDA), pentacyclic glycerol carbonate (GC), glycerol -methyl ether (GE), ethanol (EtOH) and n-butanol (BuOH) and quantity of zinc stearate are placed in a 250 mL autoclave.

(26) The autoclave is hermetically sealed, and the composition formed is heated to bring its temperature to the reaction temperature. When this reaction temperature is reached the reactor is placed under atmospheric pressure and the formed composition is held at this reaction temperature under mechanical stirring at 400 rpm for 2 hours.

(27) The reaction temperature, chemical type of oligomerization initiator, weight ratio of precursor (GCME) and initiator and precursor conversion rate are given in Table 5 below.

(28) TABLE-US-00005 TABLE 5 Temperature, C. Initiator GCME/initiator, w/w Conversion, % 180 TEA 7.5 89.0 160 EA 3 84.4 180 EA 3 98.8 180 EDA 3.2 97.0 180 GC 5.5 19.8 180 GE 4.4 19.5 180 EtOH 2.2 11.4 180 BuOH 3.5 19.2

(29) Analysis by Fourier transform infrared spectroscopy of the composition obtained by treating GCME with ethanolamine (EA) shows the complete disappearance of the signal at 1794 cm.sup.1 corresponding to the carbonyl of the GCME precursor and the onset of a signal at 1750 cm.sup.1 corresponding to the carbonyl of the linear carbonic ester of the oligomer obtained.

(30) Analysis by Fourier transform infrared spectroscopy of the composition obtained by treating GCME with ethane-1,2-diamine (EDA) shows the complete disappearance of the signal at 1794 cm.sup.1 corresponding to the carbonyl of the GCME precursor and the onset of a majority signal at 1710 cm.sup.1 corresponding to the carbonyl of a urethane group and of a minority signal at 1750 cm.sup.1 corresponding to the carbonyl of the linear carbonate.

(31) TABLE-US-00006 TABLE 6 Initiator/Temperature C. Mn Mw Mz Ip EA/160 740 781 826 1.06 290 294 299 1.02 183 185 186 1.01 104 105 107 1.02 EA/180 736 760 787 1.03 418 422 427 1.01 288 290 293 1.01 177 180 183 1.02 TEA/180 421 428 438 1.02 292 295 298 1.01 170 173 175 1.01 Glycerol/180 409 411 413 1.00 298 302 305 1.01 193 195 197 1.01 Glycerol/K.sub.2CO.sub.3 637 705 821 1.11 395 398 401 1.01 291 294 296 1.01 Glycerol/ZnSO.sub.4 177 180 183 1.02

(32) Analysis by gel permeation chromatography (GPC) of the compositions obtained in Examples 9 and 10 and described in Tables 4 and 5 is reported in Table 6 above wherein: M.sub.n is the number average molecular weight of each oligomer of the composition expressed in g/mole; M.sub.w is the weight average molecular weight of each oligomer of the composition expressed in g/mole; M.sub.z is the centrifugation mean of each oligomer of the composition expressed in g/mole; I.sub.p is the polydispersity index of each oligomer of the composition.

Example 12Oligomerization of Glycerol Cyclic Carbonate Methyl Ether (GCME) Catalysed by Zinc Stearate in the Presence of an Organic Oligomerization Initiator

(33) About 30 g of GCME, ethanolamine (EA) as oligomerization initiator and a quantity of zinc stearate are placed in a 250 mL autoclave at ambient temperature.

(34) The autoclave is hermetically sealed and the composition formed is heated to bring its temperature to the reaction temperature. When this reaction temperature is reached, the reactor is placed under atmospheric pressure and the composition obtained is held at this reaction temperature under mechanical stirring at 400 rpm.

(35) The reaction temperature, molar ratio of GCME and ethanolamine and the number average molecular weight M.sub.n of each oligomer of the composition obtained (expressed in g/mole) are given in Table 7 below.

(36) TABLE-US-00007 TABLE 7 Temperature, GCMEA/EA, C. w/w Mn.sub.1 Mn.sub.2 Mn.sub.3 Mn.sub.4 180 10 691 411 290 179 200 3 682 412 288 180 180 3 736 418 288 177 160 3 740 290 183 104

(37) This description is evidently given solely as an illustrative example and it is within the reach of persons skilled in the art to make numerous modifications, variants and applications thereto without departing from the scope of the invention, for example with respect to the choice of organic oligomerization initiator, the choice of alkoxylated glycerol cyclic carbonate precursor and choice of catalyst.