CA2091687A1 - Process for the production of oligoglycerol mixtures of high diglycerol content - Google Patents
Process for the production of oligoglycerol mixtures of high diglycerol contentInfo
- Publication number
- CA2091687A1 CA2091687A1 CA 2091687 CA2091687A CA2091687A1 CA 2091687 A1 CA2091687 A1 CA 2091687A1 CA 2091687 CA2091687 CA 2091687 CA 2091687 A CA2091687 A CA 2091687A CA 2091687 A1 CA2091687 A1 CA 2091687A1
- Authority
- CA
- Canada
- Prior art keywords
- silicate compounds
- silicate
- glycerol
- diglycerol
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000000203 mixture Substances 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 title claims description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000004760 silicates Chemical class 0.000 claims abstract description 13
- 238000009833 condensation Methods 0.000 claims abstract description 10
- 230000005494 condensation Effects 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 5
- 239000011541 reaction mixture Substances 0.000 claims abstract description 5
- 239000011734 sodium Chemical group 0.000 claims description 9
- -1 silicate compound Chemical class 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 229910052681 coesite Inorganic materials 0.000 claims description 4
- 229910052906 cristobalite Inorganic materials 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 229910052682 stishovite Inorganic materials 0.000 claims description 4
- 229910052905 tridymite Inorganic materials 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 238000006482 condensation reaction Methods 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 229910052700 potassium Chemical group 0.000 claims description 3
- 239000011591 potassium Chemical group 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229960005150 glycerol Drugs 0.000 description 13
- 235000011187 glycerol Nutrition 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 7
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 2
- 229910021333 Na2Si Inorganic materials 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- AGNTUZCMJBTHOG-UHFFFAOYSA-N 3-[3-(2,3-dihydroxypropoxy)-2-hydroxypropoxy]propane-1,2-diol Chemical compound OCC(O)COCC(O)COCC(O)CO AGNTUZCMJBTHOG-UHFFFAOYSA-N 0.000 description 1
- 101100348017 Drosophila melanogaster Nazo gene Proteins 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 208000026082 sterile multifocal osteomyelitis with periostitis and pustulosis Diseases 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- JYKSTGLAIMQDRA-UHFFFAOYSA-N tetraglycerol Chemical compound OCC(O)CO.OCC(O)CO.OCC(O)CO.OCC(O)CO JYKSTGLAIMQDRA-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Cosmetics (AREA)
Abstract
Abstract Oligoglycerol mixtures of high diglycerol content can be obtained by condensation of glycerol in the presence of silicate compounds, continuous removal of the water of condensation from the reaction mixture and termination of the reaction when the quantity of water theoretically required for the formation of diglycerol has been sepa-rated.
Description
HENKE~ XGaA
Dr. Fb/49 12th Septamber 1990 ~9 1~ 8 7 Patent Application A process ~or t~q proau~tio~ o~ oligogly¢-rol m~Ytures of high ~iglycerol cont~nt This invention relates to a process for the production of oligoglycerol mixtures of high diglycerol content by condensation of glycerol in the presence of silicate com-pounds A
Diglycerol has acquired considerable significance as a starting material for the production of fatty acid esters. Fatty acid esters are used as emulsifiers in the food industry and in cosmetics and in various industrial applications, for example as lubricants or stabilizers for PVC tJ. A~. Oil. Chem. 80c. 66, 153 tl989)1.
Diglycerol is generally produced from glycerol by reaction with glycidol tFetta, 8ei~a~, Anstri¢hm~tt., 88 101 (1986)1 or epichlorohydrin l~P-A-0 333 984]. However, the reaction is not selective, in addition to which glyci-dol and epichlorohydrin are difficult to handle and call for strict works safety measures.
Alternatively, glycerol may be condensed in the presence of alkali bases. However, it is only possible in this way to obtain mixtures which, in addition to diglycer-ol, also contain higher homologs and by no means negligible quantities of unreacted glycerol.
Since the diglycerol has to be removed from these mixtures by distillation, which is extremely time-consuming and energy-intensive, the problem addressed by the present invention was to provide an improved process by which D 9261 22 ~ 916 8 7 oligoglycerol mixtures of high diglycerol content could be obtained.
The present in~ention relates to a process for the production of oligoglycerol mixture~ of high diglycerol content, characterized in that glycerol is condensed in the presence of silicate compounds, the water of condensation is continuously removed from the reaction mixture and the reaction is terminated when the quantity of water theoret-ically required for the formation of diglycerol has been separated off.
In the following, silicate compounds are understood to be a) amorphous alkali silicates corresponding to formula (r) t8io2)~(M2o)n ~I) in which M is lithium, sodium or potassium and m and Z0 n are whole or broken numbers of greater than 0, and b) crystalline alkali disilicates corresponding to formula (II) (8io2)~lM2o)~HzO)s (II) in which M and m are as defined above, n is 1 and x is 0 or an integer of 1 to 20.
The amorphous alkali silicates are the glass-like, water-soluble salts of silicic acid solidified from the melt. Their production is described, for example, in ~OMPP~8 Chem~e L~xikon, 8th ~dition, Verlag Fr~nckh-Ro~os, 8tuttgart, Vol. 6, p~ge ~593. Both alkali silicates having a low Si02 : M2O or m:n ratio ("basic" waterqlasses) and - D 9261 3 2~1687 those having a high m:n ratio ("neutral" or "acidic" water-glasses) may be used in the process according to the inven-tion. The sio2 : M20 ratio is alRo known a~ the "modulus"
of the silicate.
The crystalline alkali disilicates are also known substance~. They have a layer-like structure and may be obtained, for example, by sintering of alkali waterglass or by hydrothermal reactions tGlast-chn. ~-r., 37 19~ ~1964)].
Suitable alkali disilicates, which catalyze the autoconden-sation of glycerol in the process according to the inven-tion, are for example makatite (Na2Si~09 5 H2O), kenyaite (Na2Si220~ 10 HzO) or ilerite (Na2Si~O" 9 HzO) tAmer.
Mineral. 38, 163 ~1953)].
Silicate compounds corresponding to formulae (I) and ~I~), in which M stands for sodium and x is 0 and of which the modulus, i.e. the m:n ratio, is from 1.9 to 4 and preferably from 1.9 to 2.5 have proved to be particularly active catalysts in the condensation of glycerol to oligo-glycerols of high diglycerol content~
The silicate compounds may be used as solids or even in the form of aqueous solutions having solids contents of 1 to 80% by weight and preferably 30 to 60% by weight, based on the silicate compound.
The silicate compounds are used in quantities of 1 to 10% by weight and preferably in quantities of 2 to 5% by weight, based on the glycerol, in the condensation reac-tion. The condensation of the glycerol is carried out at temperatures of 200 to 260-C and preferably at temperatures o~ 240 to 2SO-C.
To carry out the condensation reaction, the glycerol and the silicate compound are initially introduced and are heated to the reaction temperature in an inert gas atmos-phere. T~ shift the equilibrium, the water of condensation for~ed is removed, for example through a water separator.
The reaction is terminated when the quantity of water D 9261 4 ~9~687 theoretically required for the formation o~ diglycerol has been separated. I~ the catalysts are used in the form o~
aqueous solutions in the condensatlon reaction, their water content must be taken into account when calculating the S quantity o~ water Or condensation reguired for th~ ~orma-tion o~ diglycerol. In general, thQ reaction time i~ 1 to 30 h and pre~erably 3 to 15 h. The catalyst may be sepa-rated from the reaction mixture by, for example, filtration or centrifugation. For a number of applications, this may even be unnecessary. The diglycerol is removed from the oligoglycerol mixture formed, for example by distillation in a high vacuum. For a number of applications, however, the oligoglycerol mixture~ according to the invention may be used without further separation.
The following Examples are intended to illustrate the invention without limiting it in any way.
~xample~
Exam~l~ 1 to 6: Comparison Example 1 G-n-ral prooedur- ~or th- pro~uction o~ oligoglycerol miYtur-~ of hlg~ d~gly¢erol content 184 g (2 mol) glycerol (99.5% by weight) were intro-duced into a 250 ml three-necked flask equipped with a reflux condenser, water separator and internal thermometer and 2 to 5% by weight of a silicate compound were added.
The reaction mixture was heated to 240-C in a nitrogen atmosphere, the water of condensation being removed through the water separator. The reaction was terminated after the quantity required for the formation of diglycerol had been separated. The composition of the oligoglycerol mixture was determined by HPLC. Particulars of the catalysts, the test procedure and the product compositions are shown in Table 1. In Comparison Example Cl, potassium hydroxide was used instead of a silicate compound.
~ 9261 5 2091~87 Table 1:
Test procedures and product compositiona Percentages as % by weight Ex. Catalyst Modulus SC Q~ t Gly ~i ~Li Tetra % % h t % % %
.
1 Na silicate* 2.03 100 2.4 7 20 41 20 10 2 ~a silicate* 2.03 100 5.0 7 27 41 16 7 3 Na silicate# 2.03 55 5.0 8.5 26 40 18 8 4 Na silicate# 2.40 47 5.015 15 37 23 12 Na silicate# 3.35 36 5.025 13 37 23 12 6 ~a disilicate+ 1.94 100 3.0 8 25 42 17 7 C1 KOH - 100 2.4 7 32 29 16 9 . _ _ Legend: Modulus = ratio by weight of SiO2 to NazO
QU = quantity of catalyst used, based on gly-cerol SC = solids content of the catalyst t = reaction time Gly = glycerol Di = diglycerol Tri = triglycerol ~etra = tetraglycerol * = spray-dried, amorphous # = aqueous solution + - anhydrous, crystalline, ~-modification
Dr. Fb/49 12th Septamber 1990 ~9 1~ 8 7 Patent Application A process ~or t~q proau~tio~ o~ oligogly¢-rol m~Ytures of high ~iglycerol cont~nt This invention relates to a process for the production of oligoglycerol mixtures of high diglycerol content by condensation of glycerol in the presence of silicate com-pounds A
Diglycerol has acquired considerable significance as a starting material for the production of fatty acid esters. Fatty acid esters are used as emulsifiers in the food industry and in cosmetics and in various industrial applications, for example as lubricants or stabilizers for PVC tJ. A~. Oil. Chem. 80c. 66, 153 tl989)1.
Diglycerol is generally produced from glycerol by reaction with glycidol tFetta, 8ei~a~, Anstri¢hm~tt., 88 101 (1986)1 or epichlorohydrin l~P-A-0 333 984]. However, the reaction is not selective, in addition to which glyci-dol and epichlorohydrin are difficult to handle and call for strict works safety measures.
Alternatively, glycerol may be condensed in the presence of alkali bases. However, it is only possible in this way to obtain mixtures which, in addition to diglycer-ol, also contain higher homologs and by no means negligible quantities of unreacted glycerol.
Since the diglycerol has to be removed from these mixtures by distillation, which is extremely time-consuming and energy-intensive, the problem addressed by the present invention was to provide an improved process by which D 9261 22 ~ 916 8 7 oligoglycerol mixtures of high diglycerol content could be obtained.
The present in~ention relates to a process for the production of oligoglycerol mixture~ of high diglycerol content, characterized in that glycerol is condensed in the presence of silicate compounds, the water of condensation is continuously removed from the reaction mixture and the reaction is terminated when the quantity of water theoret-ically required for the formation of diglycerol has been separated off.
In the following, silicate compounds are understood to be a) amorphous alkali silicates corresponding to formula (r) t8io2)~(M2o)n ~I) in which M is lithium, sodium or potassium and m and Z0 n are whole or broken numbers of greater than 0, and b) crystalline alkali disilicates corresponding to formula (II) (8io2)~lM2o)~HzO)s (II) in which M and m are as defined above, n is 1 and x is 0 or an integer of 1 to 20.
The amorphous alkali silicates are the glass-like, water-soluble salts of silicic acid solidified from the melt. Their production is described, for example, in ~OMPP~8 Chem~e L~xikon, 8th ~dition, Verlag Fr~nckh-Ro~os, 8tuttgart, Vol. 6, p~ge ~593. Both alkali silicates having a low Si02 : M2O or m:n ratio ("basic" waterqlasses) and - D 9261 3 2~1687 those having a high m:n ratio ("neutral" or "acidic" water-glasses) may be used in the process according to the inven-tion. The sio2 : M20 ratio is alRo known a~ the "modulus"
of the silicate.
The crystalline alkali disilicates are also known substance~. They have a layer-like structure and may be obtained, for example, by sintering of alkali waterglass or by hydrothermal reactions tGlast-chn. ~-r., 37 19~ ~1964)].
Suitable alkali disilicates, which catalyze the autoconden-sation of glycerol in the process according to the inven-tion, are for example makatite (Na2Si~09 5 H2O), kenyaite (Na2Si220~ 10 HzO) or ilerite (Na2Si~O" 9 HzO) tAmer.
Mineral. 38, 163 ~1953)].
Silicate compounds corresponding to formulae (I) and ~I~), in which M stands for sodium and x is 0 and of which the modulus, i.e. the m:n ratio, is from 1.9 to 4 and preferably from 1.9 to 2.5 have proved to be particularly active catalysts in the condensation of glycerol to oligo-glycerols of high diglycerol content~
The silicate compounds may be used as solids or even in the form of aqueous solutions having solids contents of 1 to 80% by weight and preferably 30 to 60% by weight, based on the silicate compound.
The silicate compounds are used in quantities of 1 to 10% by weight and preferably in quantities of 2 to 5% by weight, based on the glycerol, in the condensation reac-tion. The condensation of the glycerol is carried out at temperatures of 200 to 260-C and preferably at temperatures o~ 240 to 2SO-C.
To carry out the condensation reaction, the glycerol and the silicate compound are initially introduced and are heated to the reaction temperature in an inert gas atmos-phere. T~ shift the equilibrium, the water of condensation for~ed is removed, for example through a water separator.
The reaction is terminated when the quantity of water D 9261 4 ~9~687 theoretically required for the formation o~ diglycerol has been separated. I~ the catalysts are used in the form o~
aqueous solutions in the condensatlon reaction, their water content must be taken into account when calculating the S quantity o~ water Or condensation reguired for th~ ~orma-tion o~ diglycerol. In general, thQ reaction time i~ 1 to 30 h and pre~erably 3 to 15 h. The catalyst may be sepa-rated from the reaction mixture by, for example, filtration or centrifugation. For a number of applications, this may even be unnecessary. The diglycerol is removed from the oligoglycerol mixture formed, for example by distillation in a high vacuum. For a number of applications, however, the oligoglycerol mixture~ according to the invention may be used without further separation.
The following Examples are intended to illustrate the invention without limiting it in any way.
~xample~
Exam~l~ 1 to 6: Comparison Example 1 G-n-ral prooedur- ~or th- pro~uction o~ oligoglycerol miYtur-~ of hlg~ d~gly¢erol content 184 g (2 mol) glycerol (99.5% by weight) were intro-duced into a 250 ml three-necked flask equipped with a reflux condenser, water separator and internal thermometer and 2 to 5% by weight of a silicate compound were added.
The reaction mixture was heated to 240-C in a nitrogen atmosphere, the water of condensation being removed through the water separator. The reaction was terminated after the quantity required for the formation of diglycerol had been separated. The composition of the oligoglycerol mixture was determined by HPLC. Particulars of the catalysts, the test procedure and the product compositions are shown in Table 1. In Comparison Example Cl, potassium hydroxide was used instead of a silicate compound.
~ 9261 5 2091~87 Table 1:
Test procedures and product compositiona Percentages as % by weight Ex. Catalyst Modulus SC Q~ t Gly ~i ~Li Tetra % % h t % % %
.
1 Na silicate* 2.03 100 2.4 7 20 41 20 10 2 ~a silicate* 2.03 100 5.0 7 27 41 16 7 3 Na silicate# 2.03 55 5.0 8.5 26 40 18 8 4 Na silicate# 2.40 47 5.015 15 37 23 12 Na silicate# 3.35 36 5.025 13 37 23 12 6 ~a disilicate+ 1.94 100 3.0 8 25 42 17 7 C1 KOH - 100 2.4 7 32 29 16 9 . _ _ Legend: Modulus = ratio by weight of SiO2 to NazO
QU = quantity of catalyst used, based on gly-cerol SC = solids content of the catalyst t = reaction time Gly = glycerol Di = diglycerol Tri = triglycerol ~etra = tetraglycerol * = spray-dried, amorphous # = aqueous solution + - anhydrous, crystalline, ~-modification
Claims (8)
1. A process for the production of Oligoglycerol mixtures of high diglycerol content, characterised in the glycerol is condensed in the presence of silicate compounds, the water of condensation is continuously removed from the reaction mixture and the reaction is terminated when the quantity of water theoretically required for the formation of diglycerol has been separated off.
2. A process as claimed in claim 1, characterized in that amorphous alkali silicates corresponding to formula (I) (SiO2)m(M2O)n (I) in which M is lithium, sodium or potassium and m and n are whole or broken numbers of greater than O, are used as the silicate compounds.
3. A process as claimed in claim 1, characterized in that crystalline alkali disilicates corresponding to formula (II) (SiO2)m(M2O)n(H2O)x (II) in which M is lithium, sodium or potassium, m is a whole or broken number of greater than 0, n is 1 and x is O or an integer of 1 to 20, are used as the silicate compounds.
4. A process as claimed in at least one of claims 1 to 3, characterized in that silicate compounds corresponding to formula (I) or (II), in which M is sodium, are used.
5. A process as claimed in at least one of claims 1 to 4, characterized in that silicate compounds corresponding to formula (I) or (II), of which the modulus is 1.9 to 4, are used.
6. A process as claimed in at least one of claims 1 to 5, characterized in that the silicate compounds are used in the form of aqueous solutions having solids contents of 1 to 80% by weight , based on the silicate compound.
7. A process as claimed in at least one claims 1 to 6 characterized in that the silicate compounds are used in quantities if 1 to 10% by weight, based on the glycerol.
8. A process as claimed in at least one of claims 1 to 6, characterized in that the condensation reaction is carried out at temperatures of 200 to 260°C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19904029323 DE4029323A1 (en) | 1990-09-15 | 1990-09-15 | METHOD FOR THE PRODUCTION OF OLIGOGLYCERINE MIXTURES WITH A HIGH DIGLYCERINE CONTENT |
| DEP4029323.8 | 1990-09-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2091687A1 true CA2091687A1 (en) | 1992-03-16 |
Family
ID=6414330
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2091687 Abandoned CA2091687A1 (en) | 1990-09-15 | 1991-09-06 | Process for the production of oligoglycerol mixtures of high diglycerol content |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0548104A1 (en) |
| JP (1) | JPH06500773A (en) |
| CA (1) | CA2091687A1 (en) |
| DE (1) | DE4029323A1 (en) |
| WO (1) | WO1992005133A1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5349094A (en) * | 1992-06-12 | 1994-09-20 | Henkel Kommanditgesellschaft Auf Aktien | Process for the production of oligoglycerol mixtures of increased diglycerol content |
| DE4409569C1 (en) * | 1994-03-21 | 1995-08-10 | Henkel Kgaa | New poly:glycerol poly:ricinoleate ester(s) |
| DE4420516C2 (en) * | 1994-06-13 | 1998-10-22 | Henkel Kgaa | Polyglycerol polyhydroxystearates |
| EP0732318B1 (en) * | 1995-03-15 | 2003-11-19 | Nexus A/S | A process of preparing oligomeric and/or polymeric polyol compounds and their use in the production of emulsifying agents and surfactants |
| DE19533539A1 (en) | 1995-09-11 | 1997-03-13 | Henkel Kgaa | O / W emulsifiers |
| DE19641604C1 (en) | 1996-10-09 | 1998-03-12 | Goldschmidt Ag Th | Polyglycerol partial esters of fatty acids and polyfunctional carboxylic acids, their preparation and use |
| ES2612140T3 (en) | 2012-12-14 | 2017-05-12 | Cognis Ip Management Gmbh | Polyglycerin surfactant derivatives |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB265147A (en) * | 1926-01-27 | 1928-02-09 | Henkel & Cie Gmbh | Improved manufacture of a glycerine poor in poly-glycerines and containing di-glycerine |
| US2487208A (en) * | 1946-12-23 | 1949-11-08 | Colgate Palmolive Peet Co | Preparation of diglycerol |
-
1990
- 1990-09-15 DE DE19904029323 patent/DE4029323A1/en not_active Withdrawn
-
1991
- 1991-09-06 EP EP19910914912 patent/EP0548104A1/en not_active Withdrawn
- 1991-09-06 CA CA 2091687 patent/CA2091687A1/en not_active Abandoned
- 1991-09-06 JP JP3514348A patent/JPH06500773A/en active Pending
- 1991-09-06 WO PCT/EP1991/001696 patent/WO1992005133A1/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| WO1992005133A1 (en) | 1992-04-02 |
| EP0548104A1 (en) | 1993-06-30 |
| JPH06500773A (en) | 1994-01-27 |
| DE4029323A1 (en) | 1992-03-19 |
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