DE3721003C1 - Process for the preparation of polyglycerols - Google Patents
Process for the preparation of polyglycerolsInfo
- Publication number
- DE3721003C1 DE3721003C1 DE19873721003 DE3721003A DE3721003C1 DE 3721003 C1 DE3721003 C1 DE 3721003C1 DE 19873721003 DE19873721003 DE 19873721003 DE 3721003 A DE3721003 A DE 3721003A DE 3721003 C1 DE3721003 C1 DE 3721003C1
- Authority
- DE
- Germany
- Prior art keywords
- glycerol
- diglycerol
- mixture
- alkali
- weight
- 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.)
- Expired
Links
- 229920000223 polyglycerol Polymers 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 159
- 235000011187 glycerol Nutrition 0.000 claims abstract description 60
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 claims abstract description 47
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000000203 mixture Substances 0.000 claims abstract description 30
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 16
- SSZWWUDQMAHNAQ-UHFFFAOYSA-N 3-chloropropane-1,2-diol Chemical compound OCC(O)CCl SSZWWUDQMAHNAQ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 14
- 229910001514 alkali metal chloride Inorganic materials 0.000 claims abstract description 7
- 150000002314 glycerols Chemical class 0.000 claims abstract description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract 4
- 150000001340 alkali metals Chemical class 0.000 claims abstract 4
- 239000003513 alkali Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 claims description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 2
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 238000004062 sedimentation Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 241001026509 Kata Species 0.000 claims 1
- 238000004821 distillation Methods 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 229940105990 diglycerin Drugs 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 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 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- DSEKYWAQQVUQTP-UHFFFAOYSA-N Cerin Natural products CC12CCC3(C)C4CC(C)(C)CCC4(C)CCC3(C)C2CCC2(C)C1CC(O)C(=O)C2C DSEKYWAQQVUQTP-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- XYAUIVRRMJYYHR-UHFFFAOYSA-N acetic acid;propane-1,2,3-triol Chemical compound CC(O)=O.OCC(O)CO XYAUIVRRMJYYHR-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 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
- C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Aus der DE-OS 24 55 327 ist bereits ein Verfahren zur Herstellung von Polyglycerinen (gegebenenfalls mit geringem Anteil an cyclischen Komponenten) durch sauer katalysierte Umsetzung von Glycerinen in der Wärme bekannt, wobei das Glycerin in Gegen wart von Schwefelsäure und Glycerinacetat unterhalb von 20 mm Hg zum Polyglycerin kondensiert wird. Nachteilig ist bei diesem Verfahren die Bildung von Nebenprodukten wie Acrolein und Schwefelsäureester. Ein weiterer Nachteil besteht in der notwendigen Verwendung von absolut reinem Glycerin, da sonst eine starke Verfärbung der Ansätze durch die heiße Schwefelsäure erfolgt.DE-OS 24 55 327 is already a process for the production of polyglycerols (if necessary with a small amount of cyclic components) through acid-catalyzed conversion of glycerols known in the warmth, with the glycerin in counter were from sulfuric acid and glycerin acetate below of 20 mm Hg is condensed to polyglycerol. The disadvantage of this process is the formation of By-products such as acrolein and sulfuric acid esters. Another disadvantage is the necessary Use absolutely pure glycerin, otherwise a strong discoloration of the approaches due to the hot Sulfuric acid.
Ziel und Aufgabe der vorliegenden Erfindung war es, diese Nachteile zu vermeiden und ein Verfahren zu finden, das unter geringem apparativen Aufwand so wie ohne weitere Zusätze von Hilfsmitteln die Herstellung von Polyglycerinen ermöglicht.The aim and object of the present invention was to to avoid these disadvantages and to have a procedure find that with little equipment as without the addition of any aids Production of polyglycerols enables.
Erfindungsgemäß wurde festgestellt, daß diesen Zie len und Aufgaben ein Verfahren zur Herstellung von Polyglycerinen (gegebenenfalls mit geringem Anteil an cyclischen Komponenten) durch Umsetzung von Gly cerinen in der Wärme, gerecht wird, das dadurch gekennzeichnet ist, daß Glycerin und/oder Diglycerin bei Temperaturen von 340K bis 410K mit gasförmigem Chlorwasserstoff oder mit konzentrierter Salzsäure zu einem Gemisch, beste hend im wesentlichen aus α-Monochlorhydrin des Glycerins oder des Diglycerins und Glycerin und/ oder Diglycerin umgesetzt und das entstandene Ge misch oder das aus dem Gemisch abgetrennte α- Monochlorhydrin des Glycerins oder Diglycerins bei Temperaturen von 320K bis 410K zu Alkaliglyceri nolat und/oder Alkalidiglycerinolat gegeben wird, wonach das so hergestellte Glycerin- und/oder Diglycerin-Polyglyceringemisch von den entstandenen Alkalichloriden sowie das Glycerin und/oder Diglycerin von dem Polyglycerin getrennt werden und gegebenenfalls nach vollendeter Reaktion oder nach der Bildung der Polyglycerine ein Teil des ent standenen Alkalichlorids durch an sich bekannte physikalische Verfahren, vorzugsweise durch Sedi mentation und/oder Zentrifugation als Feststoff und der andere Teil nach Zugabe von Wasser über Ionen austauscher in an sich bekannter Weise vom ent standenen Polyglyceringemisch beispielsweise gemäß dem Verfahren der DE-OS 34 10 520, abgetrennt wird.According to the invention it was found that these objectives and tasks are a process for the preparation of polyglycerols (possibly with a small proportion of cyclic components) by reacting glycerols in the heat, which is characterized in that glycerol and / or diglycerol at temperatures from 340K to 410K with gaseous hydrogen chloride or with concentrated hydrochloric acid to form a mixture consisting essentially of α- monochlorohydrin of glycerol or of diglycerol and glycerol and / or diglycerol and the resulting mixture or the α -monochlorohydrin separated from the mixture Glycerol or diglycerol at temperatures of 320K to 410K is added to alkali glycerol and / or alkali diglycerol, after which the glycerol and / or diglycerol-polyglycerol mixture thus prepared is separated from the resulting alkali metal chlorides, and the glycerol and / or diglycerol is separated from the polyglycerol and optionally after completed R eaction or after the formation of the polyglycerols part of the resulting alkali metal chloride by physical methods known per se, preferably by sedimentation and / or centrifugation as a solid and the other part after addition of water via ion exchanger in a manner known per se from the resulting polyglycerol mixture for example, according to the method of DE-OS 34 10 520, is separated.
Die Umsetzung des Glycerins und/oder Diglycerins mit gasförmigem Chlorwasserstoff oder mit konzen trierter Salzsäure erfolgt dabei in Gegenwart eines Katalysators, vorzugsweise einer flüssigen gesät tigten C1-C3 Carbonsäure, in einer Konzentration des Katalysators (bezogen auf die Gesamtgewichts menge des eingesetzten Glycerins und/oder Diglyce rins von 0,05 bis 3 Gew.-%, vorzugsweise 0,5 bis 2 Gew.-%.The reaction of the glycerol and / or diglycerol with gaseous hydrogen chloride or with concentrated hydrochloric acid is carried out in the presence of a catalyst, preferably a liquid saturated C 1 -C 3 carboxylic acid, in a concentration of the catalyst (based on the total weight of the glycerol used and / or Diglyce rins from 0.05 to 3 wt .-%, preferably 0.5 to 2 wt .-%.
Gemäß einer bevorzugten Ausführungsform des erfin dungsgemäßen Verfahrens wird das Glycerin und/oder Diglycerin bei Temperaturen von 340K bis 410K mit gasförmigem Chlorwasserstoff oder mit konzentrier ter Salzsäure in Gegenwart eines Katalysators umge setzt und das entstandene Gemisch oder das aus dem Gemisch abgetrennte α-Monochlorhydrin des Glyce rins oder Diglycerins bei Temperaturen von 320K bis 410K zu einem Alkaliglycerinolat und/ oder Alkalidiglycerinolat, das eine alkalisch rea gierende Substanz, vorzugsweise Alkalihydroxid, enthält, gegeben, wonach das so hergestellte Glyce rin- und/oder Diglycerin-Polyglyceringemisch von den entstandenen Alkalichloriden sowie das Glycerin und/oder Diglycerin von dem Polyglycerin getrennt werden.According to a preferred embodiment of the process according to the invention, the glycerol and / or diglycerol is reacted at temperatures from 340K to 410K with gaseous hydrogen chloride or with concentrated hydrochloric acid in the presence of a catalyst and the resulting mixture or the α- monochlorohydrin of the glyce separated from the mixture rins or diglycerins at temperatures of 320K to 410K to an alkali glycerol enolate and / or alkali diglycerol enolate, which contains an alkaline-reacting substance, preferably alkali metal hydroxide, is added, after which the glycine and / or diglycerol-polyglycerol mixture thus produced from the resulting alkali metal chlorides and that Glycerin and / or diglycerin are separated from the polyglycerin.
Nach einer bevorzugten Ausführungsform weist das mit gasförmigem Chlorwasserstoff oder mit konzen trierter Salzsäure umzusetzende Glycerin und/oder Diglycerin einen Glycerin- und/oder Diglycerin gehalt von mehr als 80 Gew.-%, vorzugsweise mehr als 90 Gew.-%, auf. Das nicht umgesetzte Glycerin sowie gegebenenfalls ein Teil des Diglycerins werden vorzugsweise durch fraktionierte Destillation von dem Polyglycerin getrennt.According to a preferred embodiment, this with gaseous hydrogen chloride or with conc hydrochloric acid to be converted and / or Diglycerin a glycerin and / or diglycerin content of more than 80 wt .-%, preferably more than 90% by weight. The unreacted glycerin and optionally part of the diglycerol are preferably by fractional Distillation separated from the polyglycerol.
Das eingesetzte Alkaliglycerinolat und/oder Alkali diglycerinolat weist einen Alkaliglycerinolat- oder Alkalidiglycerinolatgehalt von mehr als 80 Gew.-%, vorzugsweise mehr als 90 Gew.-%, auf und enthält vorzugsweise zusätzlich einen alkalisch reagieren den Bestandteil, vorzugsweise Alkalihydroxid.The alkali glycerol enolate and / or alkali used diglycerinolate has an alkali glycerol or Alkali diglycerol enolate content of more than 80% by weight, preferably more than 90 wt .-%, and contains preferably react additionally with an alkaline the ingredient, preferably alkali hydroxide.
Als Chlorwasserstoffgas wird im Rahmen des Verfah rens reiner Chlorwasserstoff oder ein Chlorwasser stoffgasgemisch, vorzugsweise ein Chlorwasserstoff gasgemisch, das bei der Vinylchloridherstellung und/oder Allylchloridherstellung anfällt, einge setzt.As hydrogen chloride gas in the process rens pure hydrogen chloride or a chlorine water Gas mixture, preferably a hydrogen chloride gas mixture used in the production of vinyl chloride and / or allyl chloride production occurs puts.
Als konzentrierte Salzsäure wird eine Salzsäure eingesetzt, die ein Gehalt von 10 bis 40 Gew.-%, vorzugsweise 30 bis 35 Gew.-%, HCl aufweist. As concentrated hydrochloric acid is a hydrochloric acid used, the content of 10 to 40 wt .-%, preferably 30 to 35 wt .-%, HCl.
Nach einer bevorzugten Ausführungsform des erfin dungsgemäßen Verfahrens wird das α-Mono chlorhydrin des Glycerins und/oder Diglycerins in das vorgelegte Glycerinolat und/oder Diglycerinolat unter Umrühren zugefügt, vorzugsweise durch konti nuierliche Zugabe.According to a preferred embodiment of the process according to the invention, the α- mono chlorohydrin of glycerol and / or diglycerol is added to the glycerol enolate and / or diglycerol enolate provided with stirring, preferably by continuous addition.
Gemäß einer vorteilhaften Ausführungsform des er findungsgemäßen Verfahrens wird das a-Monochlorhy drin des Glycerins und/oder Diglycerins gleichzei tig mit dem Glycerinolat und/oder Diglycerinolat kontinuierlich in einen vorzugsweise thermostabili sierten Durchlaufreaktor eingetragen, wodurch kurze Reaktionszeiten erzielt werden können. According to an advantageous embodiment of the method according to the invention, the a- monochlorohydrin of glycerol and / or diglycerol is continuously introduced into a preferably thermostabilized continuous reactor at the same time as the glycerol enolate and / or diglycerol enolate, so that short reaction times can be achieved.
In eine Lösung von 1,104 kg 99,5%iges Glycerin (12 mol) und 31,5 g 35%ige Essigsäure wurden bei ca. 383K 2,5 h lang Chlorwasserstoff eingeleitet, wobei die Gewichtszunahme ca. 40% betrug. 500 g dieser Lösung wurden unter Rühren innerhalb von 1,25 h in einen Reaktor eingetragen, worin sich 92 g (1 mol) Glycerin, 269,4 g 50%ige Natronlauge und 160 ml destilliertes Wasser bei 393K befanden.In a solution of 1.104 kg 99.5% glycerol (12th mol) and 31.5 g of 35% acetic acid were mixed at approx. 383K hydrogen chloride introduced for 2.5 hours, the weight gain was about 40%. 500 g this solution were stirred within 1.25 h entered in a reactor, in which 92 g (1 mol) glycerin, 269.4 g 50% sodium hydroxide solution and 160 ml of distilled water was at 393K.
Nach weiteren 5 h wurde das Reaktionsgemisch mit destilliertem Wasser verdünnt, über Ionenaustausch entsalzt und abschließend im Vakuum eingedampft.After a further 5 h, the reaction mixture was mixed with diluted distilled water, via ion exchange desalted and then evaporated in vacuo.
Das Produktgemisch hatte folgende Zusammensetzung (in Gewichtsprozent):The product mixture had the following composition (in percent by weight):
Glycerin 29,1, cylisches Diglycerin 1,2, Diglycerin 31,7, cyclisches Triglycerin 1,7, Triglycerin 17,1, cyclisches Tetraglycerin 0,9, Tetraglycerin 9,1, cyclisches Pentaglycerin 0,1, Pentaglycerin 4,9, Hexaglycerin 2,8, Heptaglycerin 1,3.Glycerin 29.1, cyclic diglycerin 1.2, diglycerin 31.7, cyclic triglycerin 1.7, triglycerin 17.1, cyclic tetraglycerin 0.9, tetraglycerin 9.1, cyclic pentaglycerin 0.1, pentaglycerin 4.9, Hexaglycerin 2.8, heptaglycerin 1.3.
111 g (1 mol) α-Monochlorhydrin wurden unter Rüh ren in einen Reaktor eingetragen, worin sich 92 g (1 mol) Glycerin und 81 g 50%ige Natronlauge (1,1 mol) bei 343-358K befanden. Nach 5 min wurde das Reaktionsgemisch mit destilliertem Wasser verdünnt, über Ionenaustasucher entsalzt und abschließend im Vakuum eingedampft. Das Produktgemisch hatte fol gende Zusammensetzung (in Gew.-%): 111 g (1 mol) of α- monochlorohydrin were introduced into a reactor with stirring, in which 92 g (1 mol) of glycerol and 81 g of 50% sodium hydroxide solution (1.1 mol) were at 343-358K. After 5 min, the reaction mixture was diluted with distilled water, desalted using an ion exchanger and finally evaporated in vacuo. The product mixture had the following composition (in% by weight):
Glycerin 35,0, cyclisches Diglycerin 0,3, Diglyce rin 33,5, cyclisches Triglycerin 0,2, Triglycerin 18,0, cyclisches Tetraglycerin 0,1, Tetraglycerin 8,4, Pentaglycerin 3,4, Hexaglycerin 1,2, Heptagly cerin 0,1.Glycerin 35.0, cyclic diglycerin 0.3, diglyce rin 33.5, cyclic triglycerin 0.2, triglycerin 18.0, cyclic tetraglycerin 0.1, tetraglycerin 8.4, pentaglycerin 3.4, hexaglycerin 1.2, heptagly cerin 0.1.
111 g (1 mol) α-Monochlorhydrin wurden unter Rüh ren in einen Reaktor eingetragen, worin sich 166 g (1 mol) Diglycerin und 88 g 55%ige Natronlauge (1,1 mol) bei 343-358K befanden. Nach 5 min wurde das Reaktionsgemisch mit destilliertem Wasser verdünnt, über Ionenaustauscher entsalzt und abschließend im Vakuum eingedampft.111 g (1 mol) of α- monochlorohydrin were introduced into a reactor with stirring, in which 166 g (1 mol) of diglycerol and 88 g of 55% sodium hydroxide solution (1.1 mol) were at 343-358K. After 5 min, the reaction mixture was diluted with distilled water, desalted using an ion exchanger and finally evaporated in vacuo.
Das Produktgemisch hatte folgende Zusammensetzung (in Gew.-%):The product mixture had the following composition (in% by weight):
Glycerin 4,5, cyclisches Diglycerin 0,1, Diglycerin 35,4, cyclisches Triglycerin 0,2, Triglycerin 30,8, cyclisches Tetraglycerin 0,1, Tetraglycerin 17,5, Pentaglycerin 8,0, Hexaglycerin 3,0, Heptaglycerin 0,4.Glycerin 4.5, cyclic diglycerin 0.1, diglycerin 35.4, cyclic triglycerol 0.2, triglycerol 30.8, cyclic tetraglycerin 0.1, tetraglycerin 17.5, Pentaglycerin 8.0, hexaglycerin 3.0, heptaglycerin 0.4.
Claims (13)
- 0,05 bis 3 Gew.-%, vorzugsweise
0,5 bis 2 Gew.-%,
- 0.05 to 3% by weight, preferably
0.5 to 2% by weight,
- mehr als 80 Gew.-%, vorzugsweise
mehr als 90 Gew.-%,
- more than 80% by weight, preferably
more than 90% by weight,
- mehr als 80 Gew.-%, vorzugsweise
mehr als 90 Gew.-%,
- more than 80% by weight, preferably
more than 90% by weight,
- 10 bis 40 Gew.-%, vorzugsweise
30 bis 35 Gew.-%,
- 10 to 40% by weight, preferably
30 to 35% by weight,
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19873721003 DE3721003C1 (en) | 1987-06-25 | 1987-06-25 | Process for the preparation of polyglycerols |
| DE3811826A DE3811826A1 (en) | 1987-06-25 | 1988-04-08 | METHOD FOR PRODUCING POLYGLYCERINES |
| ES198888107269T ES2039009T3 (en) | 1987-06-25 | 1988-05-06 | PROCEDURE FOR THE PREPARATION OF POLYGLYCERINES. |
| EP88107269A EP0296341B1 (en) | 1987-06-25 | 1988-05-06 | Process for the preparation of polyglycerines |
| AT88107269T ATE86961T1 (en) | 1987-06-25 | 1988-05-06 | PROCESS FOR THE PRODUCTION OF POLYGLYCERINES. |
| DE8888107269T DE3879288D1 (en) | 1987-06-25 | 1988-05-06 | METHOD FOR PRODUCING POLYGLYCERINES. |
| JP63151352A JPS6422922A (en) | 1987-06-25 | 1988-06-21 | Production of polyglycerine |
| US07/403,831 US4973763A (en) | 1987-06-25 | 1989-09-05 | Process for the preparation of polyglycerols |
| GR920403234T GR3008143T3 (en) | 1987-06-25 | 1993-06-15 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19873721003 DE3721003C1 (en) | 1987-06-25 | 1987-06-25 | Process for the preparation of polyglycerols |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE3721003C1 true DE3721003C1 (en) | 1988-12-01 |
Family
ID=6330285
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19873721003 Expired DE3721003C1 (en) | 1987-06-25 | 1987-06-25 | Process for the preparation of polyglycerols |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE3721003C1 (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008145729A1 (en) * | 2007-06-01 | 2008-12-04 | Solvay (Societe Anonyme) | Process for manufacturing a chlorohydrin |
| US7557253B2 (en) | 2005-05-20 | 2009-07-07 | Solvay (Societe Anonyme) | Method for converting polyhydroxylated aliphatic hydrocarbons into chlorohydrins |
| US7939696B2 (en) | 2005-11-08 | 2011-05-10 | Solvay Societe Anonyme | Process for the manufacture of dichloropropanol by chlorination of glycerol |
| US8067645B2 (en) | 2005-05-20 | 2011-11-29 | Solvay (Societe Anonyme) | Process for producing a chlorhydrin from a multihydroxylated aliphatic hydrocarbon and/or ester thereof in the presence of metal salts |
| US8124814B2 (en) | 2006-06-14 | 2012-02-28 | Solvay (Societe Anonyme) | Crude glycerol-based product, process for its purification and its use in the manufacture of dichloropropanol |
| US8197665B2 (en) | 2007-06-12 | 2012-06-12 | Solvay (Societe Anonyme) | Aqueous composition containing a salt, manufacturing process and use |
| US8258350B2 (en) | 2007-03-07 | 2012-09-04 | Solvay (Societe Anonyme) | Process for the manufacture of dichloropropanol |
| US8314205B2 (en) | 2007-12-17 | 2012-11-20 | Solvay (Societe Anonyme) | Glycerol-based product, process for obtaining same and use thereof in the manufacturing of dichloropropanol |
| US8378130B2 (en) | 2007-06-12 | 2013-02-19 | Solvay (Societe Anonyme) | Product containing epichlorohydrin, its preparation and its use in various applications |
| US8415509B2 (en) | 2003-11-20 | 2013-04-09 | Solvay (Societe Anonyme) | Process for producing dichloropropanol from glycerol, the glycerol coming eventually from the conversion of animal fats in the manufacture of biodiesel |
| US8471074B2 (en) | 2007-03-14 | 2013-06-25 | Solvay (Societe Anonyme) | Process for the manufacture of dichloropropanol |
| US8507643B2 (en) | 2008-04-03 | 2013-08-13 | Solvay S.A. | Composition comprising glycerol, process for obtaining same and use thereof in the manufacture of dichloropropanol |
| US8536381B2 (en) | 2008-09-12 | 2013-09-17 | Solvay Sa | Process for purifying hydrogen chloride |
| US8715568B2 (en) | 2007-10-02 | 2014-05-06 | Solvay Sa | Use of compositions containing silicon for improving the corrosion resistance of vessels |
| US8795536B2 (en) | 2008-01-31 | 2014-08-05 | Solvay (Societe Anonyme) | Process for degrading organic substances in an aqueous composition |
| US9309209B2 (en) | 2010-09-30 | 2016-04-12 | Solvay Sa | Derivative of epichlorohydrin of natural origin |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2455327A1 (en) * | 1973-11-30 | 1975-06-12 | Procter & Gamble | PROCESS FOR PRODUCING POLYGLYCERIN |
-
1987
- 1987-06-25 DE DE19873721003 patent/DE3721003C1/en not_active Expired
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2455327A1 (en) * | 1973-11-30 | 1975-06-12 | Procter & Gamble | PROCESS FOR PRODUCING POLYGLYCERIN |
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