DE4117033A1 - Prodn. of oligo:glycerol mixts. - by condensing glycerol in presence of boron cpd. and continually removing water formed - Google Patents
Prodn. of oligo:glycerol mixts. - by condensing glycerol in presence of boron cpd. and continually removing water formedInfo
- Publication number
- DE4117033A1 DE4117033A1 DE19914117033 DE4117033A DE4117033A1 DE 4117033 A1 DE4117033 A1 DE 4117033A1 DE 19914117033 DE19914117033 DE 19914117033 DE 4117033 A DE4117033 A DE 4117033A DE 4117033 A1 DE4117033 A1 DE 4117033A1
- Authority
- DE
- Germany
- Prior art keywords
- diglycerol
- glycerol
- alpha
- weight
- mixts
- 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.)
- Withdrawn
Links
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 title claims abstract description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 10
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title 1
- 229910052796 boron Inorganic materials 0.000 title 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 4
- 235000011187 glycerol Nutrition 0.000 claims description 21
- 238000009833 condensation Methods 0.000 claims description 12
- 230000005494 condensation Effects 0.000 claims description 11
- 150000001639 boron compounds Chemical class 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 4
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- 229910021538 borax Inorganic materials 0.000 claims description 2
- 150000001642 boronic acid derivatives Chemical class 0.000 claims description 2
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 claims description 2
- HZRMTWQRDMYLNW-UHFFFAOYSA-N lithium metaborate Chemical compound [Li+].[O-]B=O HZRMTWQRDMYLNW-UHFFFAOYSA-N 0.000 claims description 2
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 2
- 239000004328 sodium tetraborate Substances 0.000 claims description 2
- JVUYWILPYBCNNG-UHFFFAOYSA-N potassium;oxido(oxo)borane Chemical compound [K+].[O-]B=O JVUYWILPYBCNNG-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002585 base Substances 0.000 abstract description 2
- 239000002537 cosmetic Substances 0.000 abstract description 2
- 239000003995 emulsifying agent Substances 0.000 abstract description 2
- 235000013305 food Nutrition 0.000 abstract description 2
- 239000000314 lubricant Substances 0.000 abstract description 2
- 239000003381 stabilizer Substances 0.000 abstract description 2
- GDTSJMKGXGJFGQ-UHFFFAOYSA-N 3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound O1B([O-])OB2OB([O-])OB1O2 GDTSJMKGXGJFGQ-UHFFFAOYSA-N 0.000 abstract 1
- 229910052783 alkali metal Inorganic materials 0.000 abstract 1
- 150000001340 alkali metals Chemical class 0.000 abstract 1
- 235000014113 dietary fatty acids Nutrition 0.000 abstract 1
- 229930195729 fatty acid Natural products 0.000 abstract 1
- 239000000194 fatty acid Substances 0.000 abstract 1
- -1 fatty acid esters Chemical class 0.000 abstract 1
- 229910052744 lithium Inorganic materials 0.000 abstract 1
- 229910052700 potassium Inorganic materials 0.000 abstract 1
- 229910052708 sodium Inorganic materials 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 11
- 229940105990 diglycerin Drugs 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 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 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- JYKSTGLAIMQDRA-UHFFFAOYSA-N tetraglycerol Chemical compound OCC(O)CO.OCC(O)CO.OCC(O)CO.OCC(O)CO JYKSTGLAIMQDRA-UHFFFAOYSA-N 0.000 description 3
- 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
- 230000000052 comparative effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 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)
Abstract
Description
Die Erfindung betrifft ein Verfahren zur Herstellung von Oligo glyceringemischen durch Kondensation von Glycerin in Gegenwart von Borverbindungen.The invention relates to a process for the preparation of oligo glycerol mixtures by condensation of glycerol in the presence of Boron compounds.
Diglycerin hat als Ausgangsmaterial für die Herstellung von Fett säureestern große Bedeutung erlangt. Derartige Ester finden Ver wendung als Emulgatoren in der Nahrungsmittelindustrie und der Kosmetik sowie in verschiedenen technischen Anwendungen, bei spielsweise als Schmierstoffe oder Stabilisatoren für PVC (J. Am. Oil. Chem. Soc. 66, 153 (1989)).Diglycerin has as a starting material for the production of fat Acid esters acquired great importance. Such esters find Ver use as emulsifiers in the food industry and the Cosmetics as well as in various technical applications, at For example, as lubricants or stabilizers for PVC (J.A. Oil., Chem. Soc., 66, 153 (1989)).
Zur Herstellung von Diglycerin wird in der Regel von Glycerin ausgegangen, das mit Glycidol (Fette, Seifen, Anstrichmitt., 88, 101 (1986)) oder Epichlorhydrin (EP 03 33 984 A1) umgesetzt wird. Die Reaktion verläuft jedoch wenig selektiv, zudem sind Glycidol und Epichlorhydrin schwer zu handhaben und stellen hohe Anforderungen an den Arbeitsschutz.For the production of diglycerol is usually of glycerol with glycidol (fats, soaps, paints., 88, 101 (1986)) or epichlorohydrin (EP 03 33 984 A1). The Reaction, however, is less selective, besides, glycidol and Epichlorohydrin difficult to handle and make high demands to occupational safety.
Alternativ hierzu kann Glycerin in Gegenwart von Alkalibasen kon densiert werden. In Abhängigkeit davon, ob die Kondensation zur Verknüpfung zweier primärer (alpha, alpha), zweier sekundärer (be ta, beta) OH-Funktionen oder einer primären und einer sekundären Hydroxylgruppe (alpha, beta) führt, unterscheidet man drei verschiedene Kondensationstypen unter denen das alpha, alpha-Diglycerin eine besondere technische Bedeutung be sitzt.Alternatively, glycerol in the presence of alkali bases kon be densified. Depending on whether the condensation to Linking two primary (alpha, alpha), two secondary (be ta, beta) OH functions or one primary and one secondary Hydroxyl group (alpha, beta) leads to a distinction between three different types of condensation among which alpha, alpha-diglycerol be of special technical importance be sitting.
Die alkalische Kondensation ist jedoch mit einer Reihe von Nach teilen behaftet. Insbesondere sind auf diesem Wege nur Gemische erhältlich, die neben Diglycerin noch höhere Homologe sowie nicht zu vernachlässigende Mengen an nichtumgesetztem Glycerin enthal ten. Das Diglycerin muß aus diesen Gemischen destillativ abge trennt werden, was mit einem hohem Aufwand an Zeit und Energie verbunden ist. Aus diesem Grunde wird die Herstellung von Oligo glyceringemischen angestrebt, die einen möglichst hohen Diglyce rinanteil aufweisen. Führt man die Eigenkondensation des Glycerins in Gegenwart von Silicaten als Katalysatoren durch, werden zwar diglycerinreiche Oligoglycerine erhalten, der Anteil an alpha, al pha-verknüpften Dimeren in diesen Gemischen ist jedoch ver gleichsweise gering.However, the alkaline condensation is with a series of after share tainted. In particular, only mixtures are in this way available, which in addition to diglycerol even higher homologs and not negligible amounts of unreacted glycerol The diglycerol must be distilled off from these mixtures be separated, resulting in a great deal of time and energy connected is. For this reason, the production of oligo Glycerenemischen sought, the highest possible Diglyce have rinanteil. Performing the self-condensation of glycerol in the presence of silicates as catalysts, though diglycerol-rich oligoglycerols obtained, the proportion of alpha, al However, pha-linked dimers in these mixtures is ver at the same time low.
Die Aufgabe der Erfindung bestand somit darin, ein Verfahren zur Herstellung von Oligoglyceringemischen zu entwickeln, das frei von den geschilderten Nachteilen ist.The object of the invention was therefore to provide a method for Production of oligoglycerine mixtures to develop, free of the disadvantages described is.
Gegenstand der Erfindung ist ein Verfahren zur Herstellung von Oligoglyceringemischen, das sich dadurch auszeichnet, daß man Glycerin in Gegenwart von Borverbindungen kondensiert, das Kon densationswasser kontinuierlich aus der Reaktionsmischung entfernt und die Reaktion abbricht, sobald die zur Bildung von Diglycerin theoretisch erforderliche Menge Wasser abgeschieden worden ist.The invention relates to a process for the preparation of Oligoglyceringemischen, which is characterized in that one Glycerol condensed in the presence of boron compounds, the Kon condensation water continuously removed from the reaction mixture and the reaction stops as soon as the formation of diglycerol theoretically required amount of water has been deposited.
Überraschenderweise wurde gefunden, daß die Verwendung von Bor verbindungen in der GlycerinkondensationSurprisingly, it has been found that the use of boron compounds in the Glycerinkondensation
- - gegenüber Alkalikatalysatoren zu Oligoglyceringemischen mit einem vergleichsweise höheren Diglycerinanteil und- Compared with alkali catalysts to Oligoglyceringemischen with a comparatively higher proportion of diglycerol and
- - gegenüber Silicatkatalysatoren zu Oligoglyceringemischen mit einem vergleichsweise höheren Gehalt an alpha,alpha-verknüpf tem Diglycerin- Compared to silicate catalysts to Oligoglyceringemischen with a comparatively higher content of alpha, alpha-linked diglycerol
führt.leads.
Unter Borverbindungen, die im Sinne des erfindungsgemäßen Verfah rens als Katalysatoren für die Glycerinkondensation in Betracht kommen, sind amorphe Alkaliborate ausgewählt aus der Gruppe, die von Lithiummetaborat, Natriummetaborat, Natriumtetraborat und Ka liummetaborat gebildet wird, zu verstehen. Bevorzugt ist der Ein satz von Natriummetaborat.Boron compounds which are used in the context of the process according to the invention as catalysts for the Glycerinkondensation into consideration come, amorphous alkali borates are selected from the group that of lithium metaborate, sodium metaborate, sodium tetraborate and Ka liummetaborat is formed to understand. Preferably, the one Set of sodium metaborate.
Die Borverbindungen können in der Kondensation in Mengen von 1 bis 10, vorzugsweise 2 bis 5 Gew.-% - bezogen auf das Glycerin - ein gesetzt werden. Die Temperatur, bei der die Kondensation des Gly cerins durchgeführt wird, kann 200 bis 260, vorzugsweise 240 bis 250°C betragen.The boron compounds may be used in the condensation in amounts of 1 to 10, preferably 2 to 5 wt .-% - based on the glycerol - a be set. The temperature at which the condensation of Gly cerins may be 200 to 260, preferably 240 to 250 ° C.
Zur Durchführung der Kondensationsreaktion werden Glycerin und Borverbindung vorgelegt und in einer Inertgasatmosphäre auf die Reaktionstemperatur erhitzt. Zur Verlagerung des Gleichgewichtes wird das entstehende Kondensationswasser beispielsweise über einen Wasserabscheider abgetrennt. Die Reaktion wird abgebrochen, wenn die zur Bildung von Diglycerin theoretisch erforderliche Menge Wasser abgeschieden worden ist. Im allgemeinen beträgt die Reak tionszeit 1 bis 30, vorzugsweise 3 bis 15 h. Die Abtrennung des Diglycerins aus dem gebildeten Oligoglyceringemisch erfolgt beispielsweise durch Destillation im Hochvakuum. Für eine Vielzahl von Anwendungen können jedoch die erfindungsgemäßen Oligoglyce ringemische ohne weitere Auftrennung eingesetzt werden.To carry out the condensation reaction, glycerol and Boron compound submitted and in an inert gas atmosphere on the Reaction temperature heated. To shift the balance For example, the resulting condensation water over a Separated water separator. The reaction is stopped when the amount theoretically required to form diglycerin Water has been separated. In general, the reac tion time 1 to 30, preferably 3 to 15 h. The separation of the Diglycerol from the oligoglycerol mixture formed takes place for example by distillation in a high vacuum. For a variety however, applications of the invention may be the oligoglyce of the invention Ringemische be used without further separation.
Die nachfolgenden Beispiele sollen den Gegenstand der Erfindung näher erläutern, ohne ihn darauf einzuschränken.The following examples are intended to form the subject of the invention explain it in more detail without restricting it to it.
In einem 250-ml-Dreihalskolben mit Rückflußkühler, Wasserabschei der und Innenthermometer wurden 184 g (2 mol) Glycerin (99,5gew.-%ig) vorgelegt und mit 4,4 g (0,07 mol) Natriummetaborat (NaBO2) - entsprechend 2,4 Gew.-% bezogen auf das Glycerin - versetzt. Die Reaktionsmischung wurde in einer Stickstoffatmosphäre auf 240°C erhitzt, wobei das Kondensationswasser über den Wasserabscheider entfernt wurde. Die Reaktion wurde abgebrochen, nachdem die für die Bildung von Diglycerin erforderliche Menge abgeschieden worden war. Die Zusammensetzung des Oligoglyceringemisches wurde mittels HPLC ermittelt.In a 250 ml three-necked flask with reflux condenser, Wasserabschei and internal thermometer 184 g (2 mol) of glycerol (99.5 wt .-% strength) were introduced and with 4.4 g (0.07 mol) of sodium metaborate (NaBO 2 ) - corresponding to 2.4 wt .-% based on the glycerol - added. The reaction mixture was heated to 240 ° C in a nitrogen atmosphere, with the condensation water removed via the water separator. The reaction was stopped after the amount required for the formation of diglycerol had been removed. The composition of the oligoglycerol mixture was determined by HPLC.
Analog Beispiel 1 wurden 184 g Glycerin in Gegenwart von 4,4 g (0,08 mol) Kaliumhydroxid - entsprechend 2,4 Gew.-% bezogen auf das Glycerin - kondensiert.Analogously to Example 1, 184 g of glycerol in the presence of 4.4 g (0.08 mol) of potassium hydroxide - corresponding to 2.4 wt .-% based on the glycerin - condenses.
Analog Beispiel 1 wurden 184 g Glycerin in Gegenwart von 4,4 g (0,03 mol) Natriumsilicat (Portil(R) AW, Modul : 2,03, Fa. Henkel KGaA) - entsprechend 2,4 Gew.-% bezogen auf das Glycerin - kon densiert.Analogously to Example 1, 184 g of glycerol in the presence of 4.4 g (0.03 mol) of sodium silicate (Portil (R) AW, modulus: 2.03, Fa. Henkel KGaA) - corresponding to 2.4 wt .-% based on the glycerol - condensed kon.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19914117033 DE4117033A1 (en) | 1991-05-24 | 1991-05-24 | Prodn. of oligo:glycerol mixts. - by condensing glycerol in presence of boron cpd. and continually removing water formed |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19914117033 DE4117033A1 (en) | 1991-05-24 | 1991-05-24 | Prodn. of oligo:glycerol mixts. - by condensing glycerol in presence of boron cpd. and continually removing water formed |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE4117033A1 true DE4117033A1 (en) | 1992-11-26 |
Family
ID=6432362
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19914117033 Withdrawn DE4117033A1 (en) | 1991-05-24 | 1991-05-24 | Prodn. of oligo:glycerol mixts. - by condensing glycerol in presence of boron cpd. and continually removing water formed |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE4117033A1 (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4409569C1 (en) * | 1994-03-21 | 1995-08-10 | Henkel Kgaa | New poly:glycerol poly:ricinoleate ester(s) |
| EP0732318A1 (en) * | 1995-03-15 | 1996-09-18 | Nexus A/S | A process of preparing oligomeric and/or polymeric polyol compounds and their use in the production of emulsifying agents and surfactants |
| US5840943A (en) * | 1994-06-13 | 1998-11-24 | Henkel Kommanditgesellschaft Auf Aktien | Polyolpolyhydroxystearates |
| US6242499B1 (en) | 1996-10-09 | 2001-06-05 | Goldschmidt Ag | Polyglycerol partial esters of fatty acids and polyfunctional carboxylic acids, their preparation and use |
| US6264961B1 (en) | 1995-09-11 | 2001-07-24 | Henkel Kommanditgesellschaft Auf Aktien | Oil-water emulsifiers |
| EP2100871A1 (en) | 2008-03-10 | 2009-09-16 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Catalytic method for preparing lactic acid from renewable raw materials |
| WO2010111570A1 (en) * | 2009-03-27 | 2010-09-30 | E. I. Du Pont De Nemours And Company | Polyglycerol aldehydes |
| US8404779B2 (en) | 2009-03-27 | 2013-03-26 | Actamax Surgical Materials Llc | Tissue adhesive and sealant comprising polyglycerol aldehyde |
| US9474916B2 (en) | 2013-08-08 | 2016-10-25 | Evonik Degussa Gmbh | Carbamates from glycerine carbonate for pearlization |
-
1991
- 1991-05-24 DE DE19914117033 patent/DE4117033A1/en not_active Withdrawn
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4409569C1 (en) * | 1994-03-21 | 1995-08-10 | Henkel Kgaa | New poly:glycerol poly:ricinoleate ester(s) |
| US5736581A (en) * | 1994-03-21 | 1998-04-07 | Henkel Kommanditgesellschaft Auf Aktien | Polyglycerol polyricinoleates |
| US5840943A (en) * | 1994-06-13 | 1998-11-24 | Henkel Kommanditgesellschaft Auf Aktien | Polyolpolyhydroxystearates |
| EP0732318A1 (en) * | 1995-03-15 | 1996-09-18 | Nexus A/S | A process of preparing oligomeric and/or polymeric polyol compounds and their use in the production of emulsifying agents and surfactants |
| US6264961B1 (en) | 1995-09-11 | 2001-07-24 | Henkel Kommanditgesellschaft Auf Aktien | Oil-water emulsifiers |
| US6242499B1 (en) | 1996-10-09 | 2001-06-05 | Goldschmidt Ag | Polyglycerol partial esters of fatty acids and polyfunctional carboxylic acids, their preparation and use |
| EP2100871A1 (en) | 2008-03-10 | 2009-09-16 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Catalytic method for preparing lactic acid from renewable raw materials |
| DE102008013474A1 (en) | 2008-03-10 | 2009-09-24 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Catalytic process for the recovery of basic chemicals from renewable raw materials |
| WO2010111570A1 (en) * | 2009-03-27 | 2010-09-30 | E. I. Du Pont De Nemours And Company | Polyglycerol aldehydes |
| CN102361911A (en) * | 2009-03-27 | 2012-02-22 | 阿克塔马克斯手术器材有限责任公司 | Polyglyceraldehyde |
| US8404779B2 (en) | 2009-03-27 | 2013-03-26 | Actamax Surgical Materials Llc | Tissue adhesive and sealant comprising polyglycerol aldehyde |
| US8680200B2 (en) | 2009-03-27 | 2014-03-25 | Actamax Surgical Materials Llc | Polyglycerol aldehydes |
| USRE46234E1 (en) | 2009-03-27 | 2016-12-13 | Actamax Surgical Materials, Llc | Tissue adhesive and sealant comprising polyglycerol aldehyde |
| US9474916B2 (en) | 2013-08-08 | 2016-10-25 | Evonik Degussa Gmbh | Carbamates from glycerine carbonate for pearlization |
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