DE4229924A1 - Use of absorbable lactide copolymers - Google Patents
Use of absorbable lactide copolymersInfo
- Publication number
- DE4229924A1 DE4229924A1 DE4229924A DE4229924A DE4229924A1 DE 4229924 A1 DE4229924 A1 DE 4229924A1 DE 4229924 A DE4229924 A DE 4229924A DE 4229924 A DE4229924 A DE 4229924A DE 4229924 A1 DE4229924 A1 DE 4229924A1
- Authority
- DE
- Germany
- Prior art keywords
- copolymers
- lactide
- racemic
- monomers
- ratio
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
- A61L15/26—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L26/00—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
- A61L26/0009—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form containing macromolecular materials
- A61L26/0019—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form containing macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/04—Macromolecular materials
- A61L31/06—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
Description
Die vorliegende Erfindung betrifft eine Weiterentwicklung und Verbesserung der in der Patentanmeldung P 41 12 489.8 beschriebenen resorbierbaren physiologisch unbedenklichen Copolymeren aus razemischem Lactid und bestimmten Lactonen.The present invention relates to a further development and improvement in the patent application P 41 12 489.8 described resorbable physiologically harmless Copolymers of racemic lactide and certain lactones.
In der Patenanmeldung P 41 12 489.8 ist beschrieben, daß Copolymere aus razemischem Lactid und ε-Caprolacton, δ-Va lerolacton, γ-Decalacton oder β-Hydroxybuttersäure für die topische Behandlung menschlicher oder tierischer Haut geeig net sind, wobei diese Copolymeren durch die Umsetzung der Monomere im Molverhältnis Lactid zu Reaktionspartner von etwa 95 bis 70 zu 5 bis 30 unter Zugabe von Initiatoren und bei Temperaturen von etwa 150°C über eine Zeitspanne von etwa 16 bis 48 Stunden hergestellt werden.Patent application P 41 12 489.8 describes that Copolymers of racemic lactide and ε-caprolactone, δ-Va lerolactone, γ-decalactone or β-hydroxybutyric acid for the suitable for topical treatment of human or animal skin are net, these copolymers by the implementation of Monomers in a molar ratio of lactide to reactant of about 95 to 70 to 5 to 30 with the addition of initiators and at temperatures of about 150 ° C over a period of about 16 to 48 hours.
Im Verlauf weiterer Untersuchungen hat sich nunmehr heraus gestellt, daß bei einer Variation des Monomerverhältnisses und des Herstellungsverfahrens Copolymere erhalten werden können, die sich für bestimmte topische Anwendungszwecke gegenüber den im Hauptpatent beschriebenen Copolymeren vor teilhaft auszeichnen.In the course of further investigations it has now emerged asked that with a variation of the monomer ratio and the manufacturing process copolymers can be obtained can be used for certain topical applications compared to the copolymers described in the main patent award partial.
Wenn bei der Herstellung der Copolymere das Verhältnis von razemischem Lactid und ε-Caprolacton im Verhältnis von 85 bis 80 zu 20 bis 15 gewählt wird und das Verhältnis von Mono mer zu Initiator im Bereich von über 500 bis etwa 3000 zu 1 liegt, entstehen bei Verwendung von Metallcarboxylaten als Initiator sowie bei einer Polymerisationstemperatur von 150°C während einer Polymerisationszeit von 16 bis 48 Stunden Copolymere, die sich durch besonders gute Elastizität und Haftfähigkeit auszeichnen. Zur Folien verarbeitet zeichnen sich diese Polymere durch eine gute Gaspermeabilität und ein besonders gutes Haften auf der Haut aus und sind so flexibel, daß auch unter ungünstigen Bedingungen keine Rißbildung, selbst unter starker Belastung, festzustellen ist.If in the preparation of the copolymers the ratio of racemic lactide and ε-caprolactone in the ratio of 85 to 80 to 20 to 15 is selected and the ratio of mono to initiator in the range of over 500 to about 3000 1 lies when using metal carboxylates as initiator and at a polymerization temperature of 150 ° C during a polymerization time of 16 to 48 hours Copolymers that are characterized by particularly good elasticity and Excellent adherence. Draw processed for foils these polymers have good gas permeability and a particularly good adhesion to the skin and are like that flexible that even under unfavorable conditions none Crack formation, even under heavy loads is.
Anstelle von Lactid und Caprolacton kann auch eine Mischung aus razemischem Lactid, ε-Caprolacton und Glykolid im Ver hältnis von 80 zu 15 zu 5 bis 85 zu 10 zu 5 verwendet werden. Des gleichen kann anstelle von ε-Caprolacton auch Valerolac ton eingesetzt werden, ohne daß sich die hervorragenden Eigen schaften ändern.Instead of lactide and caprolactone, a mixture can also be used from racemic lactide, ε-caprolactone and glycolide in Ver Ratio of 80 to 15 to 5 to 85 to 10 to 5 can be used. The same can be done instead of ε-caprolactone also valerolac ton can be used without the outstanding changes.
Zur Herstellung von Sprays werden die Copolymere in der benö tigten Menge einfach in einem geeigneten Lösungsmittel gelöst und können dann als Aerosol versprüht werden. Geeignete Lö sungsmittel sind beispielsweise Essigester, Aceton oder andere Ester oder Ketone.To produce sprays, the copolymers are used in the amount simply dissolved in a suitable solvent and can then be sprayed as an aerosol. Suitable Lö solvents are, for example, ethyl acetate, acetone or others Esters or ketones.
In Sprayform können die Copolymere vorzugsweise als flüssiger Handschuh oder nach Beifügung entsprechender Wirkstoffe als Sonnenschutz- oder Insektenabwehrmittel benutzt werden.In spray form, the copolymers can preferably be in the form of a liquid Glove or after the addition of appropriate active ingredients as Sunscreen or insect repellent can be used.
Zur Herstellung von Folien können die Polymere bis zum Er weichen erwärmt und dann zu Folien ausgewalzt oder in üblicher Weise durch Extrudieren zu Folien definierten Dicke verarbeitet werden. In der Regel werden 5 bis 15 g des Copolymerem in 100 ml Essigester gelöst und anschließend weiterverarbeitet, beispielsweise durch Verdunsten des Lösungsmittels nach Ausgießen der Lösung auf silanisiertes Glas. Durch Zusätze von Weichmachern, die physiologisch unbedenklich sind, lassen sich Erweichungstemperatur und auch die Diffundibilität der Folien verändern.To produce films, the polymers can be used until Er soft warmed and then rolled into foils or in the usual way Way processed by extrusion to films defined thickness become. As a rule, 5 to 15 g of the copolymer are in 100 ml of ethyl acetate dissolved and then processed further, for example by evaporation of the solvent after pouring the solution on silanized glass. By adding Leave softeners that are physiologically safe itself softening temperature and also the diffusibility of the Change foils.
Durch Aufsprühen auf ein Walzwerk und anschließendes Pressen können die Copolymere auch zu einem Vlies verarbeitet werden.By spraying on a rolling mill and subsequent pressing the copolymers can also be processed into a nonwoven.
In einer weiteren bevorzugten Ausführungsform werden die Copolymere in einem geeigneten organischen Lösungsmittel wie beispielsweise Essigester mit hydrophilen Substanzen wie z. B. Lactid oder Glycerin vermischt. Nach dem Verdampfen des Lösungsmittels können die hydrophilen Substanzen mit Wasser o.a. Lösungsmitteln für die niedermolekularen Bestand teile ausgewaschen werden, wodurch eine spongiöse Struktur entsteht. Durch die spongiöse Struktur erhöht sich die Kapa zität der Wasserresorption beträchtlich. Falls erwünscht, kann auf die spongiöse Matrix zusätzlich eine Folie aus den selben Copolymeren durch kurzfristiges Erwärmen oder in ande rer bekannter Weise aufgeschweißt werden.In a further preferred embodiment, the Copolymers in a suitable organic solvent such as ethyl acetate with hydrophilic substances such as B. mixed lactide or glycerin. After evaporation of the solvent, the hydrophilic substances with Water or similar Solvents for the low molecular stock parts are washed out, creating a cancellous structure arises. The kapa increases due to the cancellous structure water absorption considerably. If desired, can also add a film to the spongy matrix same copolymers by brief heating or in other rer are known welded.
Die erfindungsgemäß hergestellten Copolymere sind, wie bereits erwähnt, besonders gut als Spray oder als Folien zur Abdeckung der Haut geeignet. In beiden Fällen können den Copolymeren vor der Verarbeitung zu Spray oder Folie lokalwirksame Antibiotika, Sonnenschutz-, Hautpflegemittel oder Insektenabwehrstoffe zugemischt werden.The copolymers produced according to the invention are, as already mentioned, particularly good as a spray or as a film for covering suitable for the skin. In both cases, the copolymers local antibiotics before spray or film processing, Sunscreen, skin care or insect repellents be added.
Im folgenden wird die Erfindung anhand eines Beispieles näher erläutert:The invention will be explained in more detail below using an example explains:
Razemisches Lactid und ε-Caprolacton werden in einem Molver hältnis von 80 zu 20 = 65,4 g zu 13,0 g langsam auf 150°C erhitzt. Durch Zugabe von 0,06 ml Zinn-II-diethylhexanoat wird die Polymerisation eingeleitet. Die Masse wird dann 16 Stunden bei 150°C im Ölbad erhitzt. Nach dem Abkühlen wird die Masse bei 70°C mit Essigester auf 1 l aufgefüllt und 36 Stunden geschüttelt. Falls erwünscht, können die Copo lymere nach der Polymerisation auch einem Waschvorgang unter zogen werden, um sie von Monomeren, kurzkettigen Oligomeren und/oder Weichmachern zu befreien. Dazu werden die Copolyme re, wie im Hauptpatent beschrieben, entweder mit der 600 bis 800fachen Menge Alkohol ausgefällt oder die Reaktions maße wird mit Wasser oder wäßrigem Alkohol ausgewaschen, da sich auch hierdurch bereits ein großer Teil der Monomere und der kurzkettigen Oligomeren entfernen läßt.Racemic lactide and ε-caprolactone are in a molver Ratio from 80 to 20 = 65.4 g to 13.0 g slowly to 150 ° C heated. By adding 0.06 ml of tin-II-diethylhexanoate the polymerization is initiated. The mass will then Heated in an oil bath at 150 ° C for 16 hours. After cooling the mass is made up to 1 l with ethyl acetate at 70 ° C and shaken for 36 hours. If desired, the copo polymers after the polymerization also under a washing process be pulled to them by monomers, short chain oligomers and / or free plasticizers. To do this, the copolyme re, as described in the main patent, either with the 600 up to 800 times the amount of alcohol precipitated or the reaction measure is washed out with water or aqueous alcohol, since this also causes a large part of the monomers and the short-chain oligomers can be removed.
Claims (3)
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4112489A DE4112489C2 (en) | 1991-04-17 | 1991-04-17 | Use of resorbable, physiologically harmless copolymers for the topical treatment of human or animal skin |
US07/906,319 US5466444A (en) | 1991-04-17 | 1992-06-29 | Resorbable, biocompatible copolymers and their use |
DE4229924A DE4229924C2 (en) | 1991-04-17 | 1992-09-08 | Use of absorbable lactide copolymers |
DE4230154A DE4230154C2 (en) | 1991-04-17 | 1992-09-09 | Use of lactide polymers to cover wounds |
GB9221071A GB2270260B (en) | 1992-06-29 | 1992-10-07 | Lactide copolymers for topical treatment of the skin |
SG1996004976A SG43181A1 (en) | 1992-09-08 | 1992-10-07 | Resorbable physiolically safe copolymers and their use |
MYPI92001833A MY108751A (en) | 1992-09-08 | 1992-10-12 | Resorbable, physiologically safe copolymers and thier use |
CA002080549A CA2080549C (en) | 1992-06-29 | 1992-10-14 | Resorbable, physiologically safe copolymers and their use |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4112489A DE4112489C2 (en) | 1991-04-17 | 1991-04-17 | Use of resorbable, physiologically harmless copolymers for the topical treatment of human or animal skin |
US07/906,319 US5466444A (en) | 1991-04-17 | 1992-06-29 | Resorbable, biocompatible copolymers and their use |
DE4229924A DE4229924C2 (en) | 1991-04-17 | 1992-09-08 | Use of absorbable lactide copolymers |
DE4230154A DE4230154C2 (en) | 1991-04-17 | 1992-09-09 | Use of lactide polymers to cover wounds |
Publications (2)
Publication Number | Publication Date |
---|---|
DE4229924A1 true DE4229924A1 (en) | 1994-03-10 |
DE4229924C2 DE4229924C2 (en) | 1995-12-07 |
Family
ID=27435174
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE4229924A Expired - Lifetime DE4229924C2 (en) | 1991-04-17 | 1992-09-08 | Use of absorbable lactide copolymers |
DE4230154A Expired - Lifetime DE4230154C2 (en) | 1991-04-17 | 1992-09-09 | Use of lactide polymers to cover wounds |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE4230154A Expired - Lifetime DE4230154C2 (en) | 1991-04-17 | 1992-09-09 | Use of lactide polymers to cover wounds |
Country Status (1)
Country | Link |
---|---|
DE (2) | DE4229924C2 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6706058B2 (en) | 2000-08-24 | 2004-03-16 | Deutsche Institute Fur Textil- Und Faserforschung Stuttgart Stiftung Des Offentlichen Rechts | Resorbable, synthetic, medical coating material, method for its manufacture and its use in medicine |
WO2022117842A1 (en) * | 2020-12-03 | 2022-06-09 | Polymedics Innovations Gmbh | Plaster composition, polymer film, spray plaster spray device, method for producing a polymer fiber nonwoven material, polymer fiber nonwoven material, and uses of the plaster composition |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2207635A1 (en) * | 1971-02-23 | 1972-08-31 | E.I. Du Pont De Nemours And Co., Wilmington, Del. (V.St.A.) | Pharmaceutical preparations containing polylactide |
US4045418A (en) * | 1975-01-28 | 1977-08-30 | Gulf Oil Corporation | Copolymers of D,L-lactide and epsilon caprolactone |
WO1984004311A1 (en) * | 1983-05-05 | 1984-11-08 | Hexcel Corp | Lactide/caprolactone polymer, method of making the same, composites thereof, and prostheses produced therefrom |
DE3820299A1 (en) * | 1987-06-16 | 1988-12-29 | Boehringer Ingelheim Kg | meso-Lactide, process for its preparation and polymers and copolymers prepared therefrom |
DE3928933A1 (en) * | 1988-08-31 | 1990-03-01 | G C Dental Ind Corp | PERIODONTIUM REGENERATING MATERIALS |
-
1992
- 1992-09-08 DE DE4229924A patent/DE4229924C2/en not_active Expired - Lifetime
- 1992-09-09 DE DE4230154A patent/DE4230154C2/en not_active Expired - Lifetime
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2207635A1 (en) * | 1971-02-23 | 1972-08-31 | E.I. Du Pont De Nemours And Co., Wilmington, Del. (V.St.A.) | Pharmaceutical preparations containing polylactide |
US4045418A (en) * | 1975-01-28 | 1977-08-30 | Gulf Oil Corporation | Copolymers of D,L-lactide and epsilon caprolactone |
WO1984004311A1 (en) * | 1983-05-05 | 1984-11-08 | Hexcel Corp | Lactide/caprolactone polymer, method of making the same, composites thereof, and prostheses produced therefrom |
DE3820299A1 (en) * | 1987-06-16 | 1988-12-29 | Boehringer Ingelheim Kg | meso-Lactide, process for its preparation and polymers and copolymers prepared therefrom |
DE3928933A1 (en) * | 1988-08-31 | 1990-03-01 | G C Dental Ind Corp | PERIODONTIUM REGENERATING MATERIALS |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6706058B2 (en) | 2000-08-24 | 2004-03-16 | Deutsche Institute Fur Textil- Und Faserforschung Stuttgart Stiftung Des Offentlichen Rechts | Resorbable, synthetic, medical coating material, method for its manufacture and its use in medicine |
WO2022117842A1 (en) * | 2020-12-03 | 2022-06-09 | Polymedics Innovations Gmbh | Plaster composition, polymer film, spray plaster spray device, method for producing a polymer fiber nonwoven material, polymer fiber nonwoven material, and uses of the plaster composition |
Also Published As
Publication number | Publication date |
---|---|
DE4230154C2 (en) | 1996-02-29 |
DE4230154A1 (en) | 1994-03-10 |
DE4229924C2 (en) | 1995-12-07 |
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