FR2862652A1 - Production of thermoreversible gel for biomedical uses e.g. as a support for active ingredients, comprises mixing poloxamer with water-miscible solvent and di-isocyanate, adding water and evaporating solvent - Google Patents
Production of thermoreversible gel for biomedical uses e.g. as a support for active ingredients, comprises mixing poloxamer with water-miscible solvent and di-isocyanate, adding water and evaporating solvent Download PDFInfo
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- FR2862652A1 FR2862652A1 FR0350890A FR0350890A FR2862652A1 FR 2862652 A1 FR2862652 A1 FR 2862652A1 FR 0350890 A FR0350890 A FR 0350890A FR 0350890 A FR0350890 A FR 0350890A FR 2862652 A1 FR2862652 A1 FR 2862652A1
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- reversible gel
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
- A61K47/34—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyesters, polyamino acids, polysiloxanes, polyphosphazines, copolymers of polyalkylene glycol or poloxamers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/0012—Galenical forms characterised by the site of application
- A61K9/0019—Injectable compositions; Intramuscular, intravenous, arterial, subcutaneous administration; Compositions to be administered through the skin in an invasive manner
- A61K9/0024—Solid, semi-solid or solidifying implants, which are implanted or injected in body tissue
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
- C08G18/4841—Polyethers containing oxyethylene units and other oxyalkylene units containing oxyethylene end groups
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- 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
- C08G2220/00—Compositions for preparing gels other than hydrogels, aerogels and xerogels
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/02—Polyalkylene oxides
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- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Medicinal Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Pharmacology & Pharmacy (AREA)
- Epidemiology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Veterinary Medicine (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Engineering & Computer Science (AREA)
- Proteomics, Peptides & Aminoacids (AREA)
- Inorganic Chemistry (AREA)
- Biomedical Technology (AREA)
- Dermatology (AREA)
- Neurosurgery (AREA)
- Polyurethanes Or Polyureas (AREA)
- Cosmetics (AREA)
- Materials For Medical Uses (AREA)
Abstract
Description
PROCEDE D'OBTENTION D'UN GEL THERMOREVERSIBLE A STRUCTUREPROCESS FOR OBTAINING A THERMOREVERSIBLE GEL WITH A STRUCTURE
TRIDIMENSIONNELLE CONTROLEE ET GEL OBTENU THREE-DIMENSIONAL CONTROLLED AND GEL OBTAINED
La présente invention concerne un procédé d'obtention d'un gel thermoréversible à structure tridimensionnelle contrôlée ainsi que le gel obtenu par ce procédé. The present invention relates to a process for obtaining a thermoreversible gel with a controlled three-dimensional structure, as well as the gel obtained by this method.
On connaît des gels thermoréversibles et notamment la famille des poloxamers 5 qui sont des terpolymères à blocs polyéthylèneglycolpolypropylèneglycolpolyéthylèneglycol. Thermo-reversible gels and in particular the family of poloxamers which are terpolymers with polyethylene glycolpolypropyleneglycolpolyethyleneglycol blocks are known.
Les applications sont connues depuis longtemps dans le domaine biomédical, comme support de principe actif pour des applications topiques sur des muqueuses par exemple ou pour des injections dans le cas d'intervention en chirurgie esthétique. The applications have been known for a long time in the biomedical field, as a carrier of active principle for topical applications on mucous membranes for example or for injections in the case of intervention in cosmetic surgery.
De tels gels sont utiles car ils ont des propriétés de thermoréversibilité en phase aqueuse et ils sont liquides à température ambiante par exemple tandis que la viscosité augmente sensiblement lorsque la température croît. Ceci permet par exemple l'introduction dans le corps humain de ces produits par injection car ce produit est fluide à faible température puis se gélifie au point d'avoir la consistance du derme par exemple. Ainsi, un gel thermoréversible peut-il être utilisé comme restructurant car il reste souple mais avec une certaine dureté. Such gels are useful because they have thermoreversible properties in the aqueous phase and are liquid at room temperature, for example, while the viscosity increases substantially as the temperature increases. This allows for example the introduction into the human body of these products by injection because this product is fluid at low temperature and then gels to the point of having the consistency of the dermis, for example. Thus, a thermoreversible gel can be used as a restructuring because it remains flexible but with a certain hardness.
Un des principaux inconvénients de ces gels est leur structure linéaire qui les 20 rend aisément diluable dans l'eau et qui, dans certaines applications, conduit à une rapide absorption par l'organisme. One of the main disadvantages of these gels is their linear structure which makes them easily dilutable in water and which, in some applications, leads to rapid absorption by the body.
2862652 2 Des perfectionnements ont été conduits afin de limiter cette vitesse de dégradation et d'absorption par l'organisme. Improvements have been made to limit this rate of degradation and absorption by the body.
Une solution consiste notamment à provoquer une réticulation, notamment en utilisant l'acide hyaluronique mais la gélification est dans ce cas non thermoréversible, si bien qu'un des avantages principaux de ces produits est perdu. On peut trouver la description de tels perfectionnements dans les brevets US 4 987 744 et US 4 957 744. One solution consists in particular in causing a crosslinking, in particular using hyaluronic acid, but the gelation is in this case not heat-reversible, so that one of the main advantages of these products is lost. The description of such improvements can be found in US Pat. Nos. 4,987,744 and 4,957,744.
Les poloxamers ont aussi été modifiés afin d'atteindre une structure tridimensionnelle comme indiqué dans le document de l'art antérieur, demande de brevet US 0 151 650. Dans ce mode de traitement des poloxamers, les bouts de chaîne de ces poloxamers portent des fonctions acrylate qui assurent ensuite une réticulation sous l'action d'un rayonnement ultraviolet par exemple. Le procédé de synthèse reste néanmoins long et comporte de nombreuses étapes de purification. The poloxamers have also been modified in order to achieve a three-dimensional structure as indicated in the document of the prior art, patent application US 0 151 650. In this poloxamers treatment mode, the end pieces of these poloxamers carry functions acrylate which then provide crosslinking under the action of ultraviolet radiation for example. The synthesis process nevertheless remains long and comprises numerous purification steps.
Un autre brevet US 6 316 011 décrit un gel à base de poloxamer dont on provoque la copolymérisation par de l'acide polyacrylique. Another US Pat. No. 6,316,011 describes a poloxamer-based gel which is copolymerized with polyacrylic acid.
Le gel obtenu conserve sa thermoréversibilité et sa dissolution dans l'eau est limitée par la présence de groupements acide acrylique. The gel obtained retains its thermoreversion and its dissolution in water is limited by the presence of acrylic acid groups.
La réticulation est une réticulation physique entre les groupements acide 20 acrylique sans liaison covalentes, ce qui tend à limiter la cohésion du gel dans le temps. The crosslinking is a physical crosslinking between acrylic acid groups without covalent bond, which tends to limit the cohesion of the gel over time.
Le but de la présente invention est de réaliser un gel qui conserve des propriétés de thermoréversibilité tout en ayant une structure tridimensionnelle contrôlée par modification d'un poloxamer. The object of the present invention is to provide a gel that retains thermoreversibility properties while having a three-dimensional structure controlled by modifying a poloxamer.
Le procédé de fabrication doit pouvoir être réalisé de façon simple et sans laisser de traces de produits incompatibles avec des applications biomédicales, cosmétiques ou pharmaceutiques notamment. The manufacturing process must be simple and without leaving traces of products incompatible with biomedical applications, cosmetic or pharmaceutical in particular.
2862652 3 Le procédé selon la présente invention peut être industrialisé et permet une reproductibilité. The process according to the present invention can be industrialized and allows reproducibility.
Le procédé selon la présente invention est maintenant décrit en détail suivant un mode de réalisation particulier, non limitatif, la figure unique annexée permettant de constater la thermoréversibilité et les différentes valeurs de viscosité atteintes en fonction de la température. The method according to the present invention is now described in detail according to a particular, non-limiting embodiment, the single figure attached to show the thermoreversion and the different viscosity values reached as a function of temperature.
Le procédé selon la présente invention. The method according to the present invention.
Dans le cas de réactions de polycondensation entre un polyisocyanate et un polyol, dont les poloxamers, on peut utiliser des catalyseurs tels que des sels d'étain ou des amines mais de tels composés sont incompatibles avec des applications biomédicales par exemple du fait que de très faibles quantités de catalyseurs n'ayant pas réagi peuvent subsister. In the case of polycondensation reactions between a polyisocyanate and a polyol, including poloxamers, it is possible to use catalysts such as tin salts or amines, but such compounds are incompatible with biomedical applications, for example because of the fact that small amounts of unreacted catalysts may remain.
D'autre part, en l'absence de catalyseur, si l'on veut obtenir une fonctionnalisation du poloxamer, il faut associer un agent très réactif. On the other hand, in the absence of a catalyst, if it is desired to obtain functionalization of the poloxamer, a very reactive agent must be associated.
Un autre paramètre à prendre en compte est la température puisque celleci au cours de la réaction doit être limitée. En effet, compte tenu que le gel initial est liquide, on peut assurer une homogénéité du mélange et une réaction complète alors que toute augmentation de la température provoque une gélification et donc une difficulté à homogénéiser le mélange du composé réactif avec le poloxamer. Another parameter to take into account is the temperature since this during the reaction must be limited. Indeed, considering that the initial gel is liquid, it can ensure homogeneity of the mixture and a complete reaction while any increase in temperature causes gellation and therefore a difficulty in homogenizing the mixture of the reactive compound with the poloxamer.
Le composé réactif retenu dans le cadre de la présente invention est de la famille des diisocyanates aromatiques et plus particulièrement le diisocyanate toluène. The reactive compound selected in the context of the present invention is from the family of aromatic diisocyanates and more particularly the toluene diisocyanate.
Les diisocyanates ont des fonctions NCO qui réagissent avec les fonctions alcools 25 du poloxamer. The diisocyanates have NCO functions which react with the alcohols functions of the poloxamer.
Le procédé consiste à faire réagir un diisocyanate, en excès, avec un poloxamer ayant des fonctions alcool, ceci en milieu solvant en l'occurrence de l'acétone. The process consists in reacting a diisocyanate, in excess, with a poloxamer having alcohol functions, this in a solvent medium, in this case acetone.
2862652 4 Le choix de ce solvant est important car il est toléré biomédicalement sous forme de traces. 2862652 4 The choice of this solvent is important because it is tolerated biomedically in the form of traces.
De plus, ce solvant est miscible dans l'eau et sa température d'évaporation est basse. In addition, this solvent is miscible in water and its evaporation temperature is low.
A température ambiante, les deux composés, avec du diisocyanate en excès, sont mélangés sous agitation dans le solvant et on obtient un composé intermédiaire qui comprend des terminaisons isocyanates NCO. At room temperature, the two compounds, with excess diisocyanate, are mixed with stirring in the solvent and an intermediate compound is obtained which comprises NCO isocyanate termini.
Il est bien précisé que le diisocyanate est ajouté en excès de préférence dans un rapport stoechiométrique de fonctions NCO/ fonctions OH du poloxamer, 10 compris entre 2 et 5. It is clearly stated that the diisocyanate is added in excess preferably in a stoichiometric ratio of NCO functions / OH functions of poloxamer, between 2 and 5.
Ce rapport NCO/OH doit être limité à des valeurs inférieures à 5 car audelà la viscosité augmente au point de perturber l'homogénéité du mélange et donc celle de la réaction. This NCO / OH ratio must be limited to values lower than 5 because the viscosity increases to the point of disturbing the homogeneity of the mixture and therefore that of the reaction.
Le produit intermédiaire est ensuite mélangé dans l'eau. The intermediate product is then mixed in water.
Le diisocyanate ayant été introduit en excès, la totalité du poloxamer a réagi et il subsiste du diisocyanate. Since the diisocyanate has been introduced in excess, all of the poloxamer has reacted and diisocyanate remains.
Quant au produit intermédiaire, c'est un polymère linéaire. As for the intermediate product, it is a linear polymer.
Pour ce produit intermédiaire, on détermine une quantité d'extrait sec sensiblement identique à celle du poloxamer de départ soit de l'ordre de 20 %. 20 De fait lors de l'introduction de l'eau, deux réactions se produisent: la première concerne la réaction du diisocyanate en excès avec l'eau, ce qui permet de participer à l'établissement du réseau en trois dimensions, - la seconde est la réaction des groupes isocyanates du produit intermédiaire entre eux qui permettent la formation du réseau 25 tridimensionnel. For this intermediate product, an amount of dry extract substantially identical to that of the starting poloxamer is determined, ie of the order of 20%. In fact, when the water is introduced, two reactions occur: the first concerns the reaction of the excess diisocyanate with water, which makes it possible to participate in the establishment of the three-dimensional network; is the reaction of the isocyanate groups of the intermediate product between them which allow the formation of the three-dimensional network.
La dernière étape est l'évaporation du solvant, en l'occurrence l'acétone. Il convient de limiter la montée en température, de préférence inférieure à 40 C, si l'évaporation est réalisée à pression atmosphérique. The last step is the evaporation of the solvent, in this case acetone. The rise in temperature, preferably less than 40 ° C., should be limited if the evaporation is carried out at atmospheric pressure.
2862652 5 Une autre solution est également l'évaporation sous vide. Another solution is also vacuum evaporation.
Le gel obtenu présente un caractère de thermoréversibilité avec des extraits secs inférieurs à 10%, plus particulièrement 5 à 6%. The gel obtained has a thermoreversible character with dry extracts less than 10%, more particularly 5 to 6%.
Dans le cas des applications médicales, le fait de disposer d'un gel avec une 5 quantité d'extrait sec réduite, permet de réaliser par exemple des injections dans le corps humain avec peu de matière. In the case of medical applications, having a gel with a reduced amount of dry extract makes it possible, for example, to inject the human body with little material.
L'intérêt est l'injection dans le cas d'une action anti-rides par exemple d'un composé avec une très faible viscosité, donc fluide et indolore à l'injection tandis que ses propriétés rhéologiques varient après injection pour devenir très visqueuses. La structure tridimensionnelle interdit ensuite son absorption par le corps. The interest is the injection in the case of an anti-wrinkle action for example of a compound with a very low viscosity, so fluid and painless to the injection while its rheological properties vary after injection to become very viscous. The three-dimensional structure then forbids its absorption by the body.
Un autre avantage est la possibilité de stérilisation du produit pour certaines applications. Another advantage is the possibility of sterilization of the product for certain applications.
Cette stérilisation peut être réalisée par irradiation, notamment par rayons 15 gamma. This sterilization can be carried out by irradiation, in particular by gamma rays.
Il ne produit aucune modification du réseau et on constate l'absence de liaisons susceptibles de réagir sous l'apport d'énergie engendré par le rayonnement, telles que des doubles liaisons. It produces no modification of the network and there is no connection capable of reacting under the energy input generated by the radiation, such as double bonds.
On note sur la courbe annexée en figure unique que la viscosité est variable en 20 fonction de la dilution et qu'elle varie sur une plage importante ne serait-ce qu'entre 5 et 6%. It is noted on the curve appended in the single figure that the viscosity is variable as a function of the dilution and that it varies over a large range of even between 5 and 6%.
Si l'on compare avec le poloxamer utilisé comme composé de départ et si l'on dilue ce poloxamer à 6%, on obtient un polymère qui est liquide quelle que soit la température. Le caractère viscosité variable avec réversibilité est perdu. If one compares with the poloxamer used as the starting compound and if one dilutes this poloxamer to 6%, one obtains a polymer which is liquid whatever the temperature. The variable viscosity with reversibility is lost.
On comprend aussi l'intérêt d'une telle dilution, car industriellement, la quantité de produit final par rapport au produit de départ est fortement augmentée. Sur les courbes expérimentales présentées, on constate à dilution égale une variation de viscosité et plus exactement un décalage du pic de viscosité maximale. Ceci peut être engendré par une faible proportion de solvant subsistant et non évaporé. The interest of such a dilution is also understood because, industrially, the quantity of final product relative to the starting product is greatly increased. On the experimental curves presented, one observes at equal dilution a variation of viscosity and more exactly a shift of peak of maximum viscosity. This can be caused by a small proportion of solvent remaining and not evaporated.
On constate aussi à la lecture des courbes que lorsque le rapport NCO/OH augmente, la viscosité en fonction de la température augmente car le réseau 5 tridimensionnel est plus dense. It can also be seen from the curves that when the NCO / OH ratio increases, the viscosity as a function of temperature increases because the three-dimensional network is denser.
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Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0350890A FR2862652B1 (en) | 2003-11-24 | 2003-11-24 | PROCESS FOR OBTAINING THERMOREVERSIBLE GEL WITH THREE-DIMENSIONAL STRUCTURE CONTROLLED AND GEL OBTAINED |
| PCT/FR2004/050611 WO2005051428A2 (en) | 2003-11-24 | 2004-11-23 | Method for obtaining a thermoreversible gel with a controlled three-dimensional structure, and gel obtained |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0350890A FR2862652B1 (en) | 2003-11-24 | 2003-11-24 | PROCESS FOR OBTAINING THERMOREVERSIBLE GEL WITH THREE-DIMENSIONAL STRUCTURE CONTROLLED AND GEL OBTAINED |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| FR2862652A1 true FR2862652A1 (en) | 2005-05-27 |
| FR2862652B1 FR2862652B1 (en) | 2006-04-28 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| FR0350890A Expired - Lifetime FR2862652B1 (en) | 2003-11-24 | 2003-11-24 | PROCESS FOR OBTAINING THERMOREVERSIBLE GEL WITH THREE-DIMENSIONAL STRUCTURE CONTROLLED AND GEL OBTAINED |
Country Status (2)
| Country | Link |
|---|---|
| FR (1) | FR2862652B1 (en) |
| WO (1) | WO2005051428A2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019175501A1 (en) | 2018-03-13 | 2019-09-19 | Safran Ceramics | Composite with oxide/oxide ceramic matrix |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102012223416A1 (en) * | 2012-12-17 | 2014-07-03 | Polymaterials Ag | Chain extended poloxamers, thermoreversible hydrogels formed therefrom with biological materials, and medical applications thereof |
| WO2016090361A1 (en) * | 2014-12-05 | 2016-06-09 | Akina, Inc. (An Indiana (Us) Corp) | Polymers for inducing 3d spheroid formation of biological cells |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6201065B1 (en) * | 1995-07-28 | 2001-03-13 | Focal, Inc. | Multiblock biodegradable hydrogels for drug delivery and tissue treatment |
-
2003
- 2003-11-24 FR FR0350890A patent/FR2862652B1/en not_active Expired - Lifetime
-
2004
- 2004-11-23 WO PCT/FR2004/050611 patent/WO2005051428A2/en active Application Filing
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6201065B1 (en) * | 1995-07-28 | 2001-03-13 | Focal, Inc. | Multiblock biodegradable hydrogels for drug delivery and tissue treatment |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019175501A1 (en) | 2018-03-13 | 2019-09-19 | Safran Ceramics | Composite with oxide/oxide ceramic matrix |
| FR3078965A1 (en) * | 2018-03-13 | 2019-09-20 | Safran Ceramics | OXIDE / OXIDE CERAMIC MATRIX COMPOSITE |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2005051428A3 (en) | 2005-07-28 |
| WO2005051428A2 (en) | 2005-06-09 |
| FR2862652B1 (en) | 2006-04-28 |
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