EP4065624A1 - Water-based hydrogel, and reaction product of isosorbide epoxide and amines - Google Patents

Water-based hydrogel, and reaction product of isosorbide epoxide and amines

Info

Publication number
EP4065624A1
EP4065624A1 EP20824305.5A EP20824305A EP4065624A1 EP 4065624 A1 EP4065624 A1 EP 4065624A1 EP 20824305 A EP20824305 A EP 20824305A EP 4065624 A1 EP4065624 A1 EP 4065624A1
Authority
EP
European Patent Office
Prior art keywords
water
hydrogel
soluble
isosorbide
epoxide
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.)
Pending
Application number
EP20824305.5A
Other languages
German (de)
French (fr)
Inventor
René SAINT-LOUP
Audrey SAHUT
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Roquette Freres SA
Original Assignee
Roquette Freres SA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Roquette Freres SA filed Critical Roquette Freres SA
Publication of EP4065624A1 publication Critical patent/EP4065624A1/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075—Macromolecular gels
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/74—Synthetic polymeric materials
    • A61K31/765—Polymers containing oxygen
    • A61K31/77—Polymers containing oxygen of oxiranes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • A61K8/042—Gels
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/86—Polyethers
    • 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
    • A61K9/0014—Skin, i.e. galenical aspects of topical compositions
    • 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
    • A61K9/06—Ointments; Bases therefor; Other semi-solid forms, e.g. creams, sticks, gels
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/26—Di-epoxy compounds heterocyclic
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/3236—Heterocylic compounds
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/10—General cosmetic use
    • 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
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins

Definitions

  • the present invention relates to a hydrogel and more particularly to a water-based hydrogel, and to the reaction product of water-soluble monomeric or polymeric isosorbide epoxide and water-soluble amine, its method of preparation and its use.
  • Hydrogels are a class of products which consist of a reversible physical or irreversible chemical network in which water can be trapped. These hydrogels are insoluble in water. Hydrogels are highly absorbent polymeric materials and are used in a variety of applications.
  • polymer hydrogels in the literature contain polyester, polyurethane or silicone groups.
  • Epoxies have been little studied in the manufacture of gels and even less in the manufacture of hydrogels. However, this involves simple and quantitative reactions at low temperatures. In addition, it is very insensitive to the presence of water, oxygen or impurities. Epoxies also exhibit excellent mechanical and thermal properties. Many epoxies and amines are available, but very few are soluble in water.
  • WO2008079440A2 describes a process for preparing a superelastic epoxy-based hydrogel by reaction between polyetheramine and a polyglycidyl ether.
  • hydrogels are their poor mechanical properties.
  • the proportion of rigid monomer or the degree of crosslinking can be increased.
  • the material becomes more fragile and has a reduced absorption capacity.
  • hydrogels prepared from epoxy polymer of natural and non-fossil origin having improved mechanical properties while being easy to obtain and retaining facilitated water absorption.
  • hydrogel based on polymers of natural and non-fossil origin such as isosorbide epoxide polymers or monomers, exhibited such characteristics.
  • the rigid bicyclic structure of the isosorbide epoxide makes it possible to improve the mechanical properties of the hydrogels which are prepared with these polymers or monomers of isosorbide epoxide, while keeping very good characteristics. absorption of water thanks to the hydrophilic nature of these compounds.
  • thermoset epoxy polymers and, more specifically, thermoset polymers obtained from renewable resources.
  • a first object of the present invention relates to a water-based hydrogel, and to the reaction product of isosorbide epoxide monomer or water-soluble polymer and water-soluble amine chosen from a di-, tri-, or polyamine water soluble.
  • a second object of the present invention relates to a process for preparing a hydrogel according to the invention comprising the following steps:
  • a final object of the present invention relates to the use of the hydrogel according to the invention in the medical, cosmetic, agricultural, optical field, in the field of water treatment, hygiene products, in separation technology or in energy.
  • water-based hydrogel and the reaction product of water-soluble monomeric or polymeric isosorbide epoxide and water-soluble amine selected from a water-soluble di-, tri-, or polyamine.
  • water-based hydrogel is meant a material consisting of a three-dimensional network obtained by crosslinking of polymer chains in which water or an oil-in-water emulsion can be trapped.
  • the three-dimensional cross-linked network, which is insoluble, is referred to in the following as the matrix of the hydrogel.
  • the hydrogel matrix is composed of monomeric or polymeric isosorbide epoxide having the following formula (I): formula (I) [0022] where n is an integer from 0 to 300, in particular from 0 to 10, and more particularly from 0 to 5.
  • the epoxide according to formula (I) can be manufactured according to the process described in application WO 2015/110758 A1.
  • Isosorbide epoxide can be a mixture of different isosorbide epoxides which differ from each other by the R substituent and / or the n index.
  • the index n can range from 0 to 300, in particular be equal to 290, 280, 270, 260, 250, 240, 230, 220, 210, 200, 190, 180, 170, 160, 150, 140 , 130, 120, 110, 100, 90, 80, 70, 60, 50, 40, 30, 20, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1.
  • the index n can be between 0 and 290, 0 and 280, 0 and 270, 0 and 260, 0 and 250, 0 and 240, 0 and 230, 0 and 220, 0 and 210, 0 and 200, 0 and 190, 0 and 180, 0 and 170, 0 and 160, 0 and 150, 0 and 140, 0 and 130, 0 and 120, 0 and 110, 0 and 100, 0 and 90, 0 and 80, 0 and 70, 0 and 60, 0 and 50, 0 and 40, 0 and 30, 0 and 20, 0 and 10, 0 and 9, 0 and 8, 0 and 7, 0 and 6, 0 and 5.
  • the index n can be between 1 and 290, 1 and 280, 1 and 270, 1 and 260, 1 and 250, 1 and 240, 1 and 230, 1 and 220, 1 and 210, 1 and 200,
  • the index n can be between 2 and 290, 2 and 280, 2 and 270, 2 and 260, 2 and 250, 2 and 240, 2 and 230, 2 and 220, 2 and 210, 2 and 200,
  • the index n can be between 3 and 290, 3 and 280, 3 and 270, 3 and 260, 3 and 250, 3 and 240, 3 and 230, 3 and 220, 3 and 210, 3 and 200,
  • the index n can be between 4 and 290, 4 and 280, 4 and 270, 4 and 260, 4 and 250, 4 and 240, 4 and 230, 4 and 220, 4 and 210, 4 and 200,
  • the index n can be between 5 and 290, 5 and 280, 5 and 270, 5 and 260, 5 and 250, 5 and 240, 5 and 230, 5 and 220, 5 and 210, 5 and 200,
  • the index n can be between 10 and 290, 10 and 280, 10 and 270, 10 and 260, 10 and 250, 10 and 240, 10 and 230, 10 and 220, 10 and 210, 10 and 200, 10 and 190, 10 and 180, 10 and 170, 10 and 160, 10 and 150, 10 and 140, 10 and 130, 10 and 120, 10 and 110, 10 and 100, 10 and 90, 10 and 80, 10 and 70, 10 and 60, 10 and 50, 10 and 40, 10 and 30, 10 and 20.
  • the monomeric or polymeric isosorbide epoxide of formula (I) is crosslinked using a crosslinking agent.
  • the crosslinking agent is a water soluble amine selected from a water soluble di-, tri-, or polyamine.
  • the water-soluble amine is chosen from amino acids such as lysine, arginine, asparagine, glutamine, isophorone diamine, diaminodiphenylsulfone, hexamethylene diamine, m-xylendiamine and polyetheramines such as diaminopolypropylene glycol (Jeffamine® D-230) and trimethylolpropane poly (oxypropylene) triamine (Jeffamine® T-403) as well as mixtures thereof.
  • amino acids such as lysine, arginine, asparagine, glutamine, isophorone diamine, diaminodiphenylsulfone, hexamethylene diamine, m-xylendiamine and polyetheramines such as diaminopolypropylene glycol (Jeffamine® D-230) and trimethylolpropane poly (oxypropylene) triamine (Jeffamine® T-403) as well as mixtures thereof.
  • the ratio of epoxide equivalent of isosorbide monomer or water-soluble polymer to the number of NH functions of the water-soluble amine is between 1: 5 and 5: 1, preferably between 1: 2 and 2: 1 and more preferably 1: 1, the optimum ratio lying between 2: 1 and 1: 2 with a maximum density for a ratio of 1: 1.
  • water demineralized water.
  • the hydrogel has a degree of hydration of 50 to 99%.
  • the hydration level is measured using the TGA: TG209F1 iris device from NETZSCH, according to the following method:
  • a few mg of product are placed in an alumina crucible.
  • a heating ramp is carried out from 25 ° C. to 300 ° C. at 10 ° C./min under inert gas (nitrogen with a flow rate of 40 ml / min).
  • the hydrogel When the hydrogel is in the presence of a stimulus to which it is sensitive, it swells or contracts. Mention may be made, as type of stimulus, of pH, temperature, enzymes or other biochemical agents. It can also swell or shrink over time, depending on the environment in which it is found.
  • the hydrogel according to the invention has the following properties:
  • the mechanical properties and the crosslinking density of the hydrogel can be adjusted during the preparation process of the hydrogel.
  • the hydrogels can have different physical forms, such as for example:
  • the hydrogel is biocompatible.
  • the hydrogel further comprises an active. All the characteristics of the hydrogel described above also apply to the hydrogel comprising an active.
  • active is meant any body, material, or substance, pure or as a mixture, of a chemical, biochemical or living nature, having a technical effect or function, in a field of industry, in particular medical, cosmetic, agricultural, optical, in the field of water treatment, hygiene products, in separation technology or in energy etc.
  • the active ingredient can be a pharmaceutical active principle which would be released under certain conditions.
  • the active ingredient can be a skin tightening molecule.
  • the active agent can be a molecule released on the surface of the eye when wearing a contact lens.
  • the active ingredient can be a decontaminant.
  • the active ingredient can be a decontaminant.
  • the active ingredient When the hydrogel is water-based, the active ingredient is dissolved in water. The solution is then captured by the meshes of the network and is finally released by syneresis.
  • the hydrogel When the hydrogel is based on an oil-in-water emulsion, the active ingredient is dissolved in the oily, discontinuous phase, emulsion. The emulsion is then captured by the meshes of the network and is finally released by syneresis.
  • the active agent is a water-soluble active agent, preferably an odorous molecule, a cosmetic active agent or a water-soluble pharmaceutical active agent. This active agent can for example be isosorbide which is known for these healing properties.
  • the hydrogel does not include an active ingredient, it makes it possible to subtract solid or particulate elements from a liquid medium containing this hydrogel.
  • This hydrogel has utility in the medical, cosmetic, agricultural, optical fields, in the field of water treatment, hygiene products, in separation technology or in energy.
  • the hydrogel can remove toxic molecules present in the human body.
  • the hydrogel can remove unwanted molecules present on the surface of the skin.
  • hydrogel can remove active ingredients from wastewater.
  • the hydrogel can subtract the surfaces of an unwanted molecule.
  • the hydrogel can subtract the molecule from a solution that one wishes to purify.
  • measuring solid or particulate elements from a liquid medium containing this hydrogel means the act of trapping, or capturing, elements present in a liquid medium and then removing them from said medium.
  • hydrogel in the medical, cosmetic, agricultural, optical field, in the field of water treatment, hygiene products, in separation technology or in energy.
  • the process for preparing a hydrogel according to the invention comprises the following steps:
  • an active is included in the hydrogel then it is prepared as above but adding the active during step 2) described above.
  • steps 1) and 2) of the process for preparing the hydrogel according to the invention can be carried out successively in this order or vice versa or simultaneously.
  • FIG. 1 is a diagram showing the kinetics of the concentration of isosorbide released into water from the preparation of Example 2.
  • Isosorbide epoxide Arugula.
  • Lysine Ajinomoto.
  • Isosorbide as an active ingredient Arugula.
  • Example 1 preparation of a hvdroael at 50% by mass of water
  • Example 2 preparation of a hvdroael at 50% by mass of water further comprising isosorbide as active ingredient
  • Example 3 relaraaae test of the preparation of Example 2
  • the hydrogel containing the isosorbide obtained according to Example 2 is then immersed in a given volume of water.
  • the released isosorbide content is determined by gas chromatography in the form of trimethylsilyl derivatives and quantified by the internal calibration method as described below
  • the hydrogel according to the invention obtained by a simple preparation process, is a good alternative to hydrogels based on a polymer of fossil origin.
  • the latter exhibits good water absorption, allowing the active ingredient it contains to be advantageously released. Because of these properties, the hydrogel according to the invention can therefore be used in various applications, in particular in the medical, cosmetic, agricultural, optical fields, water treatment, hygiene products, in technology. of separation or in energy.

Abstract

The invention relates to a water-based hydrogel, and a reaction product of a water-soluble monomer or polymer isosorbide epoxide and a water-soluble amine, to a method for the preparation and use thereof.

Description

Description Description
Titre : Hydrogel à base d’eau, et du produit de réaction d’époxyde d’isosorbide et d’amines Title: Water-based hydrogel, and reaction product of isosorbide epoxide and amines
[0001] La présente invention concerne un hydrogel et plus particulièrement, un hydrogel à base d’eau, et du produit de réaction d’époxyde d’isosorbide monomère ou polymère hydrosoluble et d’amine hydrosoluble, son procédé de préparation et son utilisation. The present invention relates to a hydrogel and more particularly to a water-based hydrogel, and to the reaction product of water-soluble monomeric or polymeric isosorbide epoxide and water-soluble amine, its method of preparation and its use.
Introduction Introduction
[0002] Les hydrogels sont une classe de produits qui sont constitués d’un réseau physique réversible ou chimique irréversible dans lequel de l’eau peut être piégée. Ces hydrogels sont insolubles dans l’eau. Les hydrogels sont des matériaux polymères hautement absorbants et sont utilisés dans diverses applications. [0002] Hydrogels are a class of products which consist of a reversible physical or irreversible chemical network in which water can be trapped. These hydrogels are insoluble in water. Hydrogels are highly absorbent polymeric materials and are used in a variety of applications.
[0003] Pour préparer des hydrogels chimiques irréversibles, plusieurs méthodes existent, par exemple la réticulation de polymères solubles dans l’eau ou le gonflement dans l’eau de réseaux polymères hydrophiles secs. [0003] To prepare irreversible chemical hydrogels, several methods exist, for example the crosslinking of water-soluble polymers or the swelling in water of dry hydrophilic polymer networks.
[0004] La majorité des hydrogels polymères dans la littérature contiennent des groupements polyesters, polyuréthanes ou silicones. The majority of polymer hydrogels in the literature contain polyester, polyurethane or silicone groups.
[0005] La chimie des époxydes a été peu étudiée dans la fabrication de gels et encore moins dans la fabrication d’hydrogels. Or celle-ci met en jeu des réactions simples et quantitatives à basses températures. De plus elle est très peu sensible à la présence d’eau, d’oxygène ou d’impuretés. Les époxydes présentent également d’excellentes propriétés mécaniques et thermiques. Un grand nombre d’époxydes et d’amines sont disponibles cependant très peu sont solubles dans l’eau. [0005] The chemistry of epoxies has been little studied in the manufacture of gels and even less in the manufacture of hydrogels. However, this involves simple and quantitative reactions at low temperatures. In addition, it is very insensitive to the presence of water, oxygen or impurities. Epoxies also exhibit excellent mechanical and thermal properties. Many epoxies and amines are available, but very few are soluble in water.
[0006] W02008079440A2 décrit un procédé de préparation d’un hydrogel super élastique à base d’époxyde par réaction entre la polyétheramine et un éther polyglycidyl. [0006] WO2008079440A2 describes a process for preparing a superelastic epoxy-based hydrogel by reaction between polyetheramine and a polyglycidyl ether.
[0007] La publication « Paul Calvert, Prabir Patra, and Deepak Duggal "Epoxy hydrogels as sensors and actuators", Proc. SPIE 6524, Electroactive Polymer Actuators and Devices (EAPAD) 2007, 65240M (4 April 2007) » décrit des hydrogels à base de diépoxydes et d'amines polyfonctionnelles hydrosolubles. Ce document décrit la préparation d’hydrogel à partir de polyamines aliphatiques et polyétheramines ayant réagi avec une solution aqueuse de polyéthylèneglycol diglycidyléther (PEGDGE). The publication "Paul Calvert, Prabir Patra, and Deepak Duggal" Epoxy hydrogels as sensors and actuators ", Proc. SPIE 6524, Electroactive Polymer Actuators and Devices (EAPAD) 2007, 65240M (4 April 2007) ”describes hydrogels based on diepoxides and water-soluble polyfunctional amines. This document describes the preparation of hydrogel from aliphatic polyamines and polyetheramines which have reacted with an aqueous solution of polyethylene glycol diglycidylether (PEGDGE).
[0008] Dans le contexte actuel de la diminution progressive des ressources fossiles, il est de plus en plus intéressant de remplacer les produits d’origine fossile par d’autres produits économiquement viables et acceptables d’un point de vue environnemental. [0008] In the current context of the progressive decrease in fossil resources, it is increasingly interesting to replace products of fossil origin with other products which are economically viable and acceptable from an environmental point of view.
[0009] De plus, l’un des inconvénients des hydrogels est leurs faibles propriétés mécaniques. Pour améliorer ces dernières, plusieurs solutions sont envisageables. La proportion de monomère rigide ou le taux de réticulation peuvent être augmentées. Cependant avec un réseau plus dense, le matériau devient plus fragile et présente une capacité d’absorption réduite. [0009] In addition, one of the drawbacks of hydrogels is their poor mechanical properties. To improve the latter, several solutions are possible. The proportion of rigid monomer or the degree of crosslinking can be increased. However, with a denser network, the material becomes more fragile and has a reduced absorption capacity.
[0010] Il est donc nécessaire de pouvoir disposer d’hydrogels préparés à partir de polymère d’époxyde d’origine naturelle et non fossile, ayant des propriétés mécaniques améliorées tout en étant faciles d’obtention et conservant une absorption d’eau facilitée. [0010] It is therefore necessary to be able to have hydrogels prepared from epoxy polymer of natural and non-fossil origin, having improved mechanical properties while being easy to obtain and retaining facilitated water absorption.
[0011] Poursuivant ses recherches par de très nombreux travaux, la société Demanderesse a trouvé qu’un hydrogel à base de polymères d’origine naturelle et non fossile, tels que les polymères ou monomères d’époxyde d’isosorbide, présentait de telles caractéristiques. Continuing its research through a great deal of work, the Applicant company has found that a hydrogel based on polymers of natural and non-fossil origin, such as isosorbide epoxide polymers or monomers, exhibited such characteristics. .
[0012] En effet, la structure bi-cyclique rigide de l’époxyde d’isosorbide permet d’améliorer les propriétés mécaniques des hydrogels qui sont préparés avec ces polymères ou monomères d’époxyde d’isosorbide, tout en gardant de très bonnes caractéristiques d’absorption de l’eau grâce au caractère hydrophile de ces composés. In fact, the rigid bicyclic structure of the isosorbide epoxide makes it possible to improve the mechanical properties of the hydrogels which are prepared with these polymers or monomers of isosorbide epoxide, while keeping very good characteristics. absorption of water thanks to the hydrophilic nature of these compounds.
[0013] D'autres caractéristiques et avantages de la présente invention apparaîtront à la lecture de la description détaillée suivante, lue conjointement avec la figure annexée. [0014] US2015/307650 A1 décrit des matériaux thermodurcissables et époxydiques d'origine végétale. Other characteristics and advantages of the present invention will become apparent on reading the following detailed description, read in conjunction with the attached figure. US2015 / 307650 A1 describes thermosetting and epoxy materials of plant origin.
[0015] US2008/009599 A1 décrit des polymères époxy thermodurcis et, plus précisément, les polymères thermodurcis issus de ressources renouvelables. [0015] US2008 / 009599 A1 describes thermoset epoxy polymers and, more specifically, thermoset polymers obtained from renewable resources.
Résumé de l’invention Summary of the invention
[0016] Un premier objet de la présente invention concerne un hydrogel à base d’eau, et du produit de réaction d’époxyde d’isosorbide monomère ou polymère hydrosoluble et d’amine hydrosoluble choisie parmi une di-, tri-, ou polyamine hydrosoluble. A first object of the present invention relates to a water-based hydrogel, and to the reaction product of isosorbide epoxide monomer or water-soluble polymer and water-soluble amine chosen from a di-, tri-, or polyamine water soluble.
[0017] Un second objet de la présente invention concerne un procédé de préparation d’un hydrogel selon l’invention comprenant les étapes suivantes : A second object of the present invention relates to a process for preparing a hydrogel according to the invention comprising the following steps:
1) Mélanger l’époxyde d’isosorbide monomère ou polymère hydrosoluble avec une amine hydrosoluble, 1) Mix the water-soluble monomer or polymer isosorbide epoxide with a water-soluble amine,
2) Ajouter au précédent mélange de l’eau, 2) Add to the previous mixture of water,
3) Mélanger jusqu’à obtenir un liquide translucide, et 3) Mix until you obtain a translucent liquid, and
4) Laisser réagir. 4) Let react.
[0018] Un dernier objet de la présente invention concerne l’utilisation de l’hydrogel selon l’invention dans le domaine médical, cosmétique, agricole, optique, dans le domaine du traitement de l’eau, des produits d’hygiène, dans la technologie de séparation ou dans l’énergie. A final object of the present invention relates to the use of the hydrogel according to the invention in the medical, cosmetic, agricultural, optical field, in the field of water treatment, hygiene products, in separation technology or in energy.
Description détaillée detailed description
[0019] Il est proposé un hydrogel à base d’eau, et du produit de réaction d’époxyde d’isosorbide monomère ou polymère hydrosoluble et d’amine hydrosoluble choisie parmi une di-, tri-, ou polyamine hydrosoluble. There is provided a water-based hydrogel, and the reaction product of water-soluble monomeric or polymeric isosorbide epoxide and water-soluble amine selected from a water-soluble di-, tri-, or polyamine.
[0020] Par « hydrogel à base d’eau», on entend un matériau constitué d’un réseau tridimensionnel obtenu par réticulation de chaînes polymères dans lequel de l’eau ou une émulsion huile dans eau peut être piégée. Le réseau tridimensionnel réticulé, qui est insoluble, est appelé dans ce qui suit matrice de l’hydrogel. [0021] Selon la présente invention la matrice de l’hydrogel est composée d’époxyde d’isosorbide monomère ou polymère présentant la formule (I) suivante : formule (I) [0022] où n est un entier de 0 à 300, en particulier de 0 à 10, et plus particulièrement de 0 à 5. By "water-based hydrogel" is meant a material consisting of a three-dimensional network obtained by crosslinking of polymer chains in which water or an oil-in-water emulsion can be trapped. The three-dimensional cross-linked network, which is insoluble, is referred to in the following as the matrix of the hydrogel. According to the present invention, the hydrogel matrix is composed of monomeric or polymeric isosorbide epoxide having the following formula (I): formula (I) [0022] where n is an integer from 0 to 300, in particular from 0 to 10, and more particularly from 0 to 5.
[0023] L’époxyde selon la formule (I) peut être fabriqué selon le procédé décrit dans la demande WO 2015/110758 A1. The epoxide according to formula (I) can be manufactured according to the process described in application WO 2015/110758 A1.
[0024] Il présente l’avantage d’être biosourcé et n’est pas un perturbateur endocrinien contrairement au bisphénol A. [0024] It has the advantage of being bio-based and is not an endocrine disruptor unlike bisphenol A.
[0025] L’époxyde d’isosorbide peut être un mélange de différents époxydes d’isosorbide qui diffèrent entre eux par le substituant R et/ou l’indice n. Isosorbide epoxide can be a mixture of different isosorbide epoxides which differ from each other by the R substituent and / or the n index.
[0026] L’indice n peut aller de 0 à 300, en particulier être égal à 290, 280, 270, 260, 250, 240, 230, 220, 210, 200, 190, 180, 170, 160, 150, 140, 130, 120, 110, 100, 90, 80, 70, 60, 50, 40, 30, 20, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1. The index n can range from 0 to 300, in particular be equal to 290, 280, 270, 260, 250, 240, 230, 220, 210, 200, 190, 180, 170, 160, 150, 140 , 130, 120, 110, 100, 90, 80, 70, 60, 50, 40, 30, 20, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1.
[0027] Selon un mode de réalisation, l’indice n peut être compris entre 0 et 290, 0 et 280, 0 et 270, 0 et 260, 0 et 250, 0 et 240, 0 et 230, 0 et 220, 0 et 210, 0 et 200, 0 et 190, 0 et 180, 0 et 170, 0 et 160, 0 et 150, 0 et 140, 0 et 130, 0 et 120, 0 et 110, 0 et 100, 0 et 90, 0 et 80, 0 et 70, 0 et 60, 0 et 50, 0 et 40, 0 et 30, 0 et 20, 0 et 10, 0 et 9, 0 et 8, 0 et 7, 0 et 6, 0 et 5. According to one embodiment, the index n can be between 0 and 290, 0 and 280, 0 and 270, 0 and 260, 0 and 250, 0 and 240, 0 and 230, 0 and 220, 0 and 210, 0 and 200, 0 and 190, 0 and 180, 0 and 170, 0 and 160, 0 and 150, 0 and 140, 0 and 130, 0 and 120, 0 and 110, 0 and 100, 0 and 90, 0 and 80, 0 and 70, 0 and 60, 0 and 50, 0 and 40, 0 and 30, 0 and 20, 0 and 10, 0 and 9, 0 and 8, 0 and 7, 0 and 6, 0 and 5.
[0028] Selon un mode de réalisation, l’indice n peut être compris entre 1 et 290, 1 et 280, 1 et 270, 1 et 260, 1 et 250, 1 et 240, 1 et 230, 1 et 220, 1 et 210, 1 et 200,According to one embodiment, the index n can be between 1 and 290, 1 and 280, 1 and 270, 1 and 260, 1 and 250, 1 and 240, 1 and 230, 1 and 220, 1 and 210, 1 and 200,
1 et 190, 1 et 180, 1 et 170, 1 et 160, 1 et 150, 1 et 140, 1 et 130, 1 et 120, 1 et 110, 1 et 100, 1 et 90, 1 et 80, 1 et 70, 1 et 60, 1 et 50, 1 et 40, 1 et 30, 1 et 20, 1 et 10, 1 et 9, 1 et 8, 1 et 7, 1 et 6, 1 et 5. 1 and 190, 1 and 180, 1 and 170, 1 and 160, 1 and 150, 1 and 140, 1 and 130, 1 and 120, 1 and 110, 1 and 100, 1 and 90, 1 and 80, 1 and 70, 1 and 60, 1 and 50, 1 and 40, 1 and 30, 1 and 20, 1 and 10, 1 and 9, 1 and 8, 1 and 7, 1 and 6, 1 and 5.
[0029] Selon un mode de réalisation, l’indice n peut être compris entre 2 et 290, 2 et 280, 2 et 270, 2 et 260, 2 et 250, 2 et 240, 2 et 230, 2 et 220, 2 et 210, 2 et 200,According to one embodiment, the index n can be between 2 and 290, 2 and 280, 2 and 270, 2 and 260, 2 and 250, 2 and 240, 2 and 230, 2 and 220, 2 and 210, 2 and 200,
2 et 190, 2 et 180, 2 et 170, 2 et 160, 2 et 150, 2 et 140, 2 et 130, 2 et 120, 2 et 110, 2 et 100, 2 et 90, 2 et 80, 2 et 70, 2 et 60, 2 et 50, 2 et 40, 2 et 30, 2 et 20, 2 et 10, 2 et 9, 2 et 8, 2 et 7, 2 et 6, 2 et 5. 2 and 190, 2 and 180, 2 and 170, 2 and 160, 2 and 150, 2 and 140, 2 and 130, 2 and 120, 2 and 110, 2 and 100, 2 and 90, 2 and 80, 2 and 70, 2 and 60, 2 and 50, 2 and 40, 2 and 30, 2 and 20, 2 and 10, 2 and 9, 2 and 8, 2 and 7, 2 and 6, 2 and 5.
[0030] Selon un mode de réalisation, l’indice n peut être compris entre 3 et 290, 3 et 280, 3 et 270, 3 et 260, 3 et 250, 3 et 240, 3 et 230, 3 et 220, 3 et 210, 3 et 200,According to one embodiment, the index n can be between 3 and 290, 3 and 280, 3 and 270, 3 and 260, 3 and 250, 3 and 240, 3 and 230, 3 and 220, 3 and 210, 3 and 200,
3 et 190, 3 et 180, 3 et 170, 3 et 160, 3 et 150, 3 et 140, 3 et 130, 3 et 120, 3 et 110, 3 et 100, 3 et 90, 3 et 80, 3 et 70, 3 et 60, 3 et 50, 3 et 40, 3 et 30, 3 et 20, 3 et 10, 3 et 9, 3 et 8, 3 et 7, 3 et 6, 3 et 5. 3 and 190, 3 and 180, 3 and 170, 3 and 160, 3 and 150, 3 and 140, 3 and 130, 3 and 120, 3 and 110, 3 and 100, 3 and 90, 3 and 80, 3 and 70, 3 and 60, 3 and 50, 3 and 40, 3 and 30, 3 and 20, 3 and 10, 3 and 9, 3 and 8, 3 and 7, 3 and 6, 3 and 5.
[0031] Selon un mode de réalisation, l’indice n peut être compris entre 4 et 290, 4 et 280, 4 et 270, 4 et 260, 4 et 250, 4 et 240, 4 et 230, 4 et 220, 4 et 210, 4 et 200,According to one embodiment, the index n can be between 4 and 290, 4 and 280, 4 and 270, 4 and 260, 4 and 250, 4 and 240, 4 and 230, 4 and 220, 4 and 210, 4 and 200,
4 et 190, 4 et 180, 4 et 170, 4 et 160, 4 et 150, 4 et 140, 4 et 130, 4 et 120, 4 et 110, 4 et 100, 4 et 90, 4 et 80, 4 et 70, 4 et 60, 4 et 50, 4 et 40, 4 et 30, 4 et 20, 4 et 10, 4 et 9, 4 et 8, 4 et 7, 4 et 6, 4 et 5. 4 and 190, 4 and 180, 4 and 170, 4 and 160, 4 and 150, 4 and 140, 4 and 130, 4 and 120, 4 and 110, 4 and 100, 4 and 90, 4 and 80, 4 and 70, 4 and 60, 4 and 50, 4 and 40, 4 and 30, 4 and 20, 4 and 10, 4 and 9, 4 and 8, 4 and 7, 4 and 6, 4 and 5.
[0032] Selon un mode de réalisation, l’indice n peut être compris entre 5 et 290, 5 et 280, 5 et 270, 5 et 260, 5 et 250, 5 et 240, 5 et 230, 5 et 220, 5 et 210, 5 et 200,According to one embodiment, the index n can be between 5 and 290, 5 and 280, 5 and 270, 5 and 260, 5 and 250, 5 and 240, 5 and 230, 5 and 220, 5 and 210, 5 and 200,
5 et 190, 5 et 180, 5 et 170, 5 et 160, 5 et 150, 5 et 140, 5 et 130, 5 et 120, 5 et 110, 5 et 100, 5 et 90, 5 et 80, 5 et 70, 5 et 60, 5 et 50, 5 et 40, 5 et 30, 5 et 20, 5 et 10, 5 et 9, 5 et 8, 5 et 7, 5 et 6. 5 and 190, 5 and 180, 5 and 170, 5 and 160, 5 and 150, 5 and 140, 5 and 130, 5 and 120, 5 and 110, 5 and 100, 5 and 90, 5 and 80, 5 and 70, 5 and 60, 5 and 50, 5 and 40, 5 and 30, 5 and 20, 5 and 10, 5 and 9, 5 and 8, 5 and 7, 5 and 6.
[0033] Selon un mode de réalisation, l’indice n peut être compris entre 10 et 290, 10 et 280, 10 et 270, 10 et 260, 10 et 250, 10 et 240, 10 et 230, 10 et 220, 10 et 210, 10 et 200, 10 et 190, 10 et 180, 10 et 170, 10 et 160, 10 et 150, 10 et 140, 10 et 130, 10 et 120, 10 et 110, 10 et 100, 10 et 90, 10 et 80, 10 et 70, 10 et 60, 10 et 50, 10 et 40, 10 et 30, 10 et 20. According to one embodiment, the index n can be between 10 and 290, 10 and 280, 10 and 270, 10 and 260, 10 and 250, 10 and 240, 10 and 230, 10 and 220, 10 and 210, 10 and 200, 10 and 190, 10 and 180, 10 and 170, 10 and 160, 10 and 150, 10 and 140, 10 and 130, 10 and 120, 10 and 110, 10 and 100, 10 and 90, 10 and 80, 10 and 70, 10 and 60, 10 and 50, 10 and 40, 10 and 30, 10 and 20.
[0034] Dans l’hydrogel, l’époxyde d’isosorbide monomère ou polymère de formule (I) est réticulé à l’aide d’un agent réticulant. L’agent réticulant est une amine hydrosoluble choisie parmi une di-, tri-, ou polyamine hydrosoluble. Selon un mode de réalisation, l’amine hydrosoluble est choisie parmi les acides aminés tels que la lysine, l’arginine, l’asparagine, la glutamine, l’isophorone diamine, diaminodiphenylsulfone, l’hexaméthylène diamine, la m-xylendiamine et les polyétheramines telles que le diaminopolypropylene glycol (Jeffamine® D-230) et le trimethylolpropane poly(oxypropylene)triamine (Jeffamine® T-403) ainsi que leurs mélanges. In the hydrogel, the monomeric or polymeric isosorbide epoxide of formula (I) is crosslinked using a crosslinking agent. The crosslinking agent is a water soluble amine selected from a water soluble di-, tri-, or polyamine. According to one embodiment, the water-soluble amine is chosen from amino acids such as lysine, arginine, asparagine, glutamine, isophorone diamine, diaminodiphenylsulfone, hexamethylene diamine, m-xylendiamine and polyetheramines such as diaminopolypropylene glycol (Jeffamine® D-230) and trimethylolpropane poly (oxypropylene) triamine (Jeffamine® T-403) as well as mixtures thereof.
[0035] Selon un mode de réalisation préféré, le ratio en équivalent époxyde d’isosorbide monomère ou polymère hydrosoluble sur le nombre de fonctions N-H de l’amine hydrosoluble est compris entre 1 :5 et 5 :1, de préférence entre 1 :2 et 2 :1 et plus préférentiellement 1 :1.Le ratio optimum se situant entre 2 :1 et 1 :2 avec un maximum de densité pour un ratio de 1 :1. According to a preferred embodiment, the ratio of epoxide equivalent of isosorbide monomer or water-soluble polymer to the number of NH functions of the water-soluble amine is between 1: 5 and 5: 1, preferably between 1: 2 and 2: 1 and more preferably 1: 1, the optimum ratio lying between 2: 1 and 1: 2 with a maximum density for a ratio of 1: 1.
[0036] Par « eau » on entend l’eau déminéralisée. Selon un mode de réalisation préféré, l’hydrogel présente un taux d’hydratation de 50 à 99 %. Le taux d’hydratation est mesuré à l’aide de l’appareil TGA : TG209F1 iris de NETZSCH, selon la méthode suivante : By "water" is meant demineralized water. According to a preferred embodiment, the hydrogel has a degree of hydration of 50 to 99%. The hydration level is measured using the TGA: TG209F1 iris device from NETZSCH, according to the following method:
Quelques mg de produit sont déposés dans un creuset alumine. On effectue une rampe de chauffe de 25°C à 300°C à 10°C/min sous gaz inerte (azote avec un débit de 40ml/min). A few mg of product are placed in an alumina crucible. A heating ramp is carried out from 25 ° C. to 300 ° C. at 10 ° C./min under inert gas (nitrogen with a flow rate of 40 ml / min).
[0037] Lorsque l’hydrogel se trouve en présence d’un stimulus auquel il est sensible, il se gonfle ou se rétracte. Comme type de stimulus on peut citer le pH, la température, les enzymes ou autres agents biochimiques. Il peut aussi se gonfler ou se rétracter au cours du temps notamment en fonction de l’environnement dans lequel il se trouve. When the hydrogel is in the presence of a stimulus to which it is sensitive, it swells or contracts. Mention may be made, as type of stimulus, of pH, temperature, enzymes or other biochemical agents. It can also swell or shrink over time, depending on the environment in which it is found.
[0038] En résumé, l’hydrogel selon l’invention présente les propriétés suivantes :In summary, the hydrogel according to the invention has the following properties:
- Biosourcé - Adaptabilité, et - Biobased - Adaptability, and
- Synérèse contrôlable. - Controllable syneresis.
[0039] Les propriétés mécaniques et la densité de réticulation de l’hydrogel peuvent être ajustées lors du procédé de préparation de l’hydrogel. [0040] Les hydrogels peuvent avoir différentes formes physiques, comme par exemple : [0039] The mechanical properties and the crosslinking density of the hydrogel can be adjusted during the preparation process of the hydrogel. The hydrogels can have different physical forms, such as for example:
- un solide mou comme une lentille de contact, - a soft solid like a contact lens,
- une poudre comprimée comme utilisé dans l’élaboration de certaines pilules et capsule pour l’administration d’actif par voie orale, - des microparticules qui peuvent servir de vecteurs pour des applications médicales, par exemple des vecteurs bio adhésifs lors de traitement de plaies, ou encore - a compressed powder as used in the preparation of certain pills and capsules for the administration of active ingredients by the oral route, - microparticles which can serve as vectors for medical applications, for example bioadhesive vectors during the treatment of wounds , or
-un revêtement spécial pour des implants. -a special coating for implants.
Selon un mode de réalisation préféré, l’hydrogel est biocompatible. [0041] Selon un autre mode de réalisation préféré, l’hydrogel comprend en outre un actif. Toutes les caractéristiques de l’hydrogel décrites précédemment s’appliquent également à l’hydrogel comprenant un actif. According to a preferred embodiment, the hydrogel is biocompatible. [0041] According to another preferred embodiment, the hydrogel further comprises an active. All the characteristics of the hydrogel described above also apply to the hydrogel comprising an active.
[0042] Par « actif » on entend tout corps, matériau, ou substance, pur ou en mélange, de nature chimique, biochimique ou vivante, ayant un effet ou fonction technique, dans un domaine de l'industrie, notamment médical, cosmétique, agricole, optique, dans le domaine du traitement de l’eau, des produits d’hygiène, dans la technologie de séparation ou dans l’énergie etc. Dans le domaine médical, l’actif peut être un principe actif pharmaceutique qui serait relargué dans certaines conditions. Dans le domaine cosmétique, l’actif peut être une molécule tenseur de la peau. Dans le domaine optique, l’actif peut être une molécule relarguée à la surface de l’œil lors du port de lentille de contact. Dans le domaine du traitement de l’eau, l’actif peut être un décontaminant. Dans le domaine des produits d’hygiènes, l’actif peut être un décontaminant. Lorsque l’hydrogel est à base d’eau, l’actif est solubilisé dans l’eau. La solution est ensuite capturée par les mailles du réseau et est enfin relargué par synérèse. Lorsque l’hydrogel est à base d’une émulsion huile dans eau, l’actif est solubilisé dans la phase huileuse, discontinue, de l’émulsion. L’émulsion est ensuite capturée par les mailles du réseau et est enfin relargué par synérèse. De préférence l’actif est un actif soluble dans l’eau, de préférence une molécule odorante, un actif cosmétique ou un actif pharmaceutique hydrosoluble. Cet actif peut par exemple être l’isosorbide qui est connu pour ces propriétés cicatrisantes. By "active" is meant any body, material, or substance, pure or as a mixture, of a chemical, biochemical or living nature, having a technical effect or function, in a field of industry, in particular medical, cosmetic, agricultural, optical, in the field of water treatment, hygiene products, in separation technology or in energy etc. In the medical field, the active ingredient can be a pharmaceutical active principle which would be released under certain conditions. In the cosmetic field, the active ingredient can be a skin tightening molecule. In the optical field, the active agent can be a molecule released on the surface of the eye when wearing a contact lens. In the field of water treatment, the active ingredient can be a decontaminant. In the field of hygiene products, the active ingredient can be a decontaminant. When the hydrogel is water-based, the active ingredient is dissolved in water. The solution is then captured by the meshes of the network and is finally released by syneresis. When the hydrogel is based on an oil-in-water emulsion, the active ingredient is dissolved in the oily, discontinuous phase, emulsion. The emulsion is then captured by the meshes of the network and is finally released by syneresis. Preferably the active agent is a water-soluble active agent, preferably an odorous molecule, a cosmetic active agent or a water-soluble pharmaceutical active agent. This active agent can for example be isosorbide which is known for these healing properties.
[0043] Dans le cas où l’hydrogel ne comprend pas d’actif, il permet de soustraire des éléments solides ou particulaires d’un milieu liquide contenant cet hydrogel. Cet hydrogel a une utilité dans le domaine médical, cosmétique, agricole, optique, dans le domaine du traitement de l’eau, des produits d’hygiène, dans la technologie de séparation ou dans l’énergie. Dans le domaine médical, l’hydrogel peut soustraire des molécules toxiques présentes dans le corps humain. Dans le domaine cosmétique, l’hydrogel peut soustraire des molécules indésirables présentes à la surface de la peau. Dans le domaine du traitement de l’eau, l’hydrogel peut soustraire des principes actifs des eaux usées. Dans le domaine des produits d’hygiènes, l’hydrogel peut soustraire les surfaces d’une molécule indésirable. Dans le domaine de la technologie de séparation, l’hydrogel peut soustraire la molécule d’une solution que l’on souhaite purifier. [0043] In the case where the hydrogel does not include an active ingredient, it makes it possible to subtract solid or particulate elements from a liquid medium containing this hydrogel. This hydrogel has utility in the medical, cosmetic, agricultural, optical fields, in the field of water treatment, hygiene products, in separation technology or in energy. In the medical field, the hydrogel can remove toxic molecules present in the human body. In cosmetics, the hydrogel can remove unwanted molecules present on the surface of the skin. In the field of water treatment, hydrogel can remove active ingredients from wastewater. In the area of hygiene products, the hydrogel can subtract the surfaces of an unwanted molecule. In the field of separation technology, the hydrogel can subtract the molecule from a solution that one wishes to purify.
[0044] On entend par «soustraire des éléments solides ou particulaires d’un milieu liquide contenant cet hydrogel», le fait de piéger, ou capturer, des éléments présents dans un milieu liquide puis de les retirer dudit milieu. The term "subtracting solid or particulate elements from a liquid medium containing this hydrogel" means the act of trapping, or capturing, elements present in a liquid medium and then removing them from said medium.
[0045] Selon un autre aspect de la présente invention, il est proposé l’utilisation d’un hydrogel dans le domaine médical, cosmétique, agricole, optique, dans le domaine du traitement de l’eau, des produits d’hygiène, dans la technologie de séparation ou dans l’énergie. According to another aspect of the present invention, there is proposed the use of a hydrogel in the medical, cosmetic, agricultural, optical field, in the field of water treatment, hygiene products, in separation technology or in energy.
[0046] Selon un autre aspect, il est proposé un procédé de préparation d’un hydrogel selon l’invention comprenant les étapes suivantes : According to another aspect, there is provided a process for preparing a hydrogel according to the invention comprising the following steps:
1) Mélanger l’époxyde d’isosorbide monomère ou polymère hydrosoluble avec une amine hydrosoluble, 1) Mix the water-soluble monomer or polymer isosorbide epoxide with a water-soluble amine,
2) Ajouter au précédent mélange de l’eau, 2) Add to the previous mixture of water,
3) Mélanger jusqu’à obtenir un liquide translucide, et 4) Laisser réagir à température ambiante ou à une température pouvant aller jusqu’à 80°C. 3) Mix until you obtain a translucent liquid, and 4) Leave to react at room temperature or at a temperature of up to 80 ° C.
[0047] Selon un mode de réalisation particulier, le procédé de préparation d’un hydrogel selon l’invention comprend les étapes suivantes : [0047] According to a particular embodiment, the process for preparing a hydrogel according to the invention comprises the following steps:
1) Mélanger l’époxyde d’isosorbide monomère ou polymère hydrosoluble avec une amine hydrosoluble, de préférence selon un ratio fonction epoxy sur fonction -NH compris entre 1 :5 et 5 :1, plus préférentiellement entre 1 :2 et 2 :1 et encore plus préférentiellement 1 :1, 1) Mix the epoxide of isosorbide monomer or water-soluble polymer with a water-soluble amine, preferably according to an epoxy function / -NH function ratio of between 1: 5 and 5: 1, more preferably between 1: 2 and 2: 1 and even more preferably 1: 1,
2) Ajouter au précédent mélange de l’eau, 2) Add to the previous mixture of water,
3) Mélanger jusqu’à obtenir un liquide translucide, 3) Mix until you obtain a translucent liquid,
4) Optionnellement, verser le liquide translucide obtenu dans un moule, 4) Optionally, pour the translucent liquid obtained into a mold,
5) Laisser réagir, de préférence à température ambiante ou à une température pouvant aller jusqu’à 80°C, et 5) Leave to react, preferably at room temperature or at a temperature of up to 80 ° C, and
6) Optionnellement, démouler l’hydrogel ainsi formé. 6) Optionally, unmold the hydrogel thus formed.
[0048] Selon un autre mode de réalisation, le procédé de préparation d’un hydrogel selon l’invention comprenant les étapes suivantes : [0048] According to another embodiment, the process for preparing a hydrogel according to the invention comprising the following steps:
1) Mélanger l’époxyde d’isosorbide monomère ou polymère hydrosoluble avec une amine hydrosoluble selon un ratio fonction epoxy sur fonction -NH compris entre 1 :5 et 5 :1, de préférence entre 1 :2 et 2 :1 et plus préférentiellement 1 :1, 1) Mix the water-soluble monomer or polymer isosorbide epoxide with a water-soluble amine according to an epoxy function / -NH function ratio of between 1: 5 and 5: 1, preferably between 1: 2 and 2: 1 and more preferably 1 : 1,
2) Ajouter au précédent mélange de l’eau, 2) Add to the previous mixture of water,
3) Mélanger jusqu’à obtenir un liquide translucide, 3) Mix until you obtain a translucent liquid,
4) Verser le liquide translucide obtenu dans un moule, 4) Pour the translucent liquid obtained into a mold,
5) Laisser réagir à température ambiante ou à une température pouvant aller jusqu’à 80°C, et 5) Leave to react at room temperature or at a temperature of up to 80 ° C, and
6) Démouler l’hydrogel ainsi formé. 6) Unmold the hydrogel thus formed.
[0049] Si un actif est inclus dans l’hydrogel alors, il est préparé comme précédemment mais en ajoutant l’actif lors de l’étape 2) ci-dessus décrite. If an active is included in the hydrogel then it is prepared as above but adding the active during step 2) described above.
[0050] Selon un autre mode de réalisation, les étapes 1) et 2) du procédé de préparation de l’hydrogel selon l’invention peuvent être réalisées successivement dans cet ordre ou inversement ou simultanément. According to another embodiment, steps 1) and 2) of the process for preparing the hydrogel according to the invention can be carried out successively in this order or vice versa or simultaneously.
Brève description des dessins [0051] D’autres caractéristiques, détails et avantages de l’invention apparaîtront à la lecture de la description détaillée ci-après, et à l’analyse des dessins annexés, sur lesquels : Brief description of the drawings Other characteristics, details and advantages of the invention will become apparent on reading the detailed description below, and on analyzing the appended drawings, in which:
Fig. 1 Fig. 1
[0052] [Fig. 1] est un diagramme montrant la cinétique de concentration d’isosorbide relargué dans l’eau à partir de la préparation de l’exemple 2. [0052] [Fig. 1] is a diagram showing the kinetics of the concentration of isosorbide released into water from the preparation of Example 2.
Exemples Examples
[0053] Réactifs : [0053] Reagents:
Epoxyde d’isosorbide : Roquette. Isosorbide epoxide: Arugula.
Lysine : Ajinomoto. Lysine: Ajinomoto.
Isosorbide en tant qu’ingrédient actif : Roquette. Isosorbide as an active ingredient: Arugula.
Eau : Eau déminéralisée. Water: Demineralized water.
[0054] Exemple 1 : préparation d’un hvdroael à 50% massique en eau [0054] Example 1: preparation of a hvdroael at 50% by mass of water
[0055] On mélange 5g d’époxyde d’isosorbide (EEW=180g/eq) (c’est à dire le produit de formule (I) avec R=H et n=0), avec 1,03g de Lysine. Puis on ajoute 6,03g d’eau déminéralisée. On mélange afin d’obtenir une préparation homogène. On verse dans un moule puis on laisse réagir à température ambiante. L’hydrogel est obtenu après 72h. On démoule l’hydrogel ainsi obtenu. 5 g of isosorbide epoxide (EEW = 180 g / eq) (ie the product of formula (I) with R = H and n = 0) are mixed with 1.03 g of Lysine. Then 6.03g of demineralized water is added. Mix to obtain a homogeneous preparation. It is poured into a mold and then left to react at room temperature. The hydrogel is obtained after 72 hours. The hydrogel thus obtained is demolded.
[0056] Exemple 2 : préparation d’un hvdroael à 50% massique en eau comprenant en outre de l’isosorbide comme ingrédient actif [0056] Example 2: preparation of a hvdroael at 50% by mass of water further comprising isosorbide as active ingredient
[0057] On mélange 5g d’époxyde d’isosorbide (EEW=180g/eq) avec 1,03g de Lysine. Puis on ajoute 6,03g d’une solution aqueuse d’isosorbide à 20% massique. On mélange afin d’obtenir une préparation homogène. On verse dans un moule puis on laisse réagir à température ambiante. L’hydrogel est obtenu après 72h. On démoule l’hydrogel renfermant l’ingrédient actif ainsi obtenu. 5g of isosorbide epoxide (EEW = 180g / eq) are mixed with 1.03g of Lysine. Then 6.03g of a 20% by weight aqueous isosorbide solution is added. Mix to obtain a homogeneous preparation. It is poured into a mold and then left to react at room temperature. The hydrogel is obtained after 72 hours. The hydrogel containing the active ingredient thus obtained is demolded.
[0058] Exemple 3 : test de relaraaae de la préparation de l’exemple 2 Example 3: relaraaae test of the preparation of Example 2
[0059] L’hydrogel renfermant l’isosorbide obtenu selon l’exemple 2 est ensuite immergé dans un volume d’eau donnée. La teneur en isosorbide relargué est déterminée par chromatographie gazeuse sous forme de dérivés triméthylsilylés et quantifiée par la méthode de l’étalonnage interne telle que décrite ci-dessous Nom de l’appareil : CPG type Varian 3800 ou Bruker 450 équipé d’un injecteur split-splitless ; d’un détecteur FID ; d’une colonne capillaire DB1 (J&W scientific réf 123-1033 ; 30m de longueur ; 0,32mm de diamètre interne ; 1 micron d’épaisseur de film. The hydrogel containing the isosorbide obtained according to Example 2 is then immersed in a given volume of water. The released isosorbide content is determined by gas chromatography in the form of trimethylsilyl derivatives and quantified by the internal calibration method as described below Device name: GC type Varian 3800 or Bruker 450 equipped with a split-splitless injector; an FID detector; a DB1 capillary column (J&W scientific ref 123-1033; 30m long; 0.32mm internal diameter; 1 micron film thickness.
[0060] Conditions d’analyses : [0060] Analysis conditions:
Température colonne : programmation de température dès l’injection de 140° à 250°C à raison de 3 °C/minute puis jusque 300°C à raison de 10°C/min. Température injecteur : 300°C Température détecteur : 300°C Column temperature: temperature programming from 140 ° to 250 ° C at the rate of 3 ° C / minute, then up to 300 ° C at the rate of 10 ° C / min. Injector temperature: 300 ° C Detector temperature: 300 ° C
Pression : 10 psi Gaz Vecteur : Hélium Mode d’injection : split avec « liner split » impératif Débit du split : 80 ml/minute Débit hydrogène : 30 ml/minute Débit d’air : 400 ml/minute Volume injecté : 1 microlitre Pressure: 10 psi Carrier gas: Helium Injection mode: split with "liner split" imperative Split flow rate: 80 ml / minute Hydrogen flow rate: 30 ml / minute Air flow rate: 400 ml / minute Volume injected: 1 microliter
Dans un bêcher de 100 ml, on pèse environ précisément 1g de produit et 50 mg d’étalon interne (aMéthyl-D-glucopyranoside). O, ajoute environ 50 ml de pyridine (4-1 ). On laisse sous agitation magnétique jusqu’à dissolution complète. In a 100 ml beaker, approximately precisely 1 g of product and 50 mg of internal standard (αMethyl-D-glucopyranoside) are weighed out. O, add about 50 ml of pyridine (4-1). Magnetically stirred until complete dissolution.
Dans un godet de 2ml à bouchon vissable, on dépose 1 ml de la solution, 1ml de pyridine et 0,3 ml de BSTFA. On bouche. On agite. On laisse au bain à sec thermostaté à 70°C pendant 30 minutes avant d’injecter 1 microlitre. In a 2 ml cup with a screw cap, 1 ml of the solution, 1 ml of pyridine and 0.3 ml of BSTFA are placed. We stop up. We stir. It is left in a dry bath thermostatically controlled at 70 ° C for 30 minutes before injecting 1 microliter.
[0061] La cinétique de concentration en isosorbide relargué dans l’eau est donnée sur la figure 1 sur laquelle le seuil de 2,5% correspond à la concentration maximale en isosorbide pouvant être mise en œuvre lors de cet essai au vu de la quantité d’isosorbide introduit et du volume d’eau connu utilisé pour l’étape de relargage. The kinetics of isosorbide concentration released in water is given in Figure 1 on which the threshold of 2.5% corresponds to the maximum concentration of isosorbide that can be implemented during this test in view of the quantity of isosorbide introduced and of the known volume of water used for the release step.
[0062] Ce test montre que l’hydrogel formé a une capacité de relargage de l’isosorbide. Ce dernier est complètement relargué au bout de 4h. [0063] En conséquence les inventeurs ont découvert que l’hydrogel selon l’invention permet de relarguer des ingrédients actifs, ce temps de relargage pouvant être ajusté en fonction de la formulation de l’hydrogel. This test shows that the hydrogel formed has an isosorbide release capacity. The latter is completely released after 4 hours. Consequently, the inventors have discovered that the hydrogel according to the invention makes it possible to release active ingredients, this release time being able to be adjusted according to the formulation of the hydrogel.
[0064] L’hydrogel selon l’invention, obtenu selon un procédé de préparation simple, est une bonne alternative aux hydrogels à base de polymère d’origine fossile. Ce dernier présente une bonne absorption de l’eau permettant de relarguer avantageusement l’ingrédient actif qu’il contient. Du fait de ces propriétés, l’hydrogel selon l’invention peut donc être utilisé dans des applications diverses, notamment dans le domaine médical, cosmétique, agricole, optique, le traitement de l’eau, les produits d’hygiène, dans la technologie de séparation ou dans l’énergie. The hydrogel according to the invention, obtained by a simple preparation process, is a good alternative to hydrogels based on a polymer of fossil origin. The latter exhibits good water absorption, allowing the active ingredient it contains to be advantageously released. Because of these properties, the hydrogel according to the invention can therefore be used in various applications, in particular in the medical, cosmetic, agricultural, optical fields, water treatment, hygiene products, in technology. of separation or in energy.

Claims

Revendications Claims
[Revendication 1] Hydrogel à base d’eau et du produit de réaction d’époxyde d’isosorbide monomère ou polymère hydrosoluble et d’amine hydrosoluble choisie parmi une di-, tri-, ou polyamine hydrosoluble. [Claim 1] A hydrogel based on water and the reaction product of water-soluble monomeric or polymeric isosorbide epoxide and water-soluble amine selected from a water-soluble di-, tri-, or polyamine.
[Revendication 2] Hydrogel selon la revendication 1, dans laquelle l’époxyde d’isosorbide monomère ou polymère hydrosoluble présente la formule (I) suivante : [Claim 2] The hydrogel of claim 1, wherein the water-soluble monomeric or polymeric isosorbide epoxide has the following formula (I):
Où n est un entier de 0 à 300, de préférence de 0 à 10, et plus préférentiellement de 0 à 5. Where n is an integer from 0 to 300, preferably from 0 to 10, and more preferably from 0 to 5.
[Revendication 3] Hydrogel selon les revendications 1 ou 2, dans lequel la di-, tri-, ou polyamine hydrosoluble est choisie parmi la lysine, l’arginine, l’asparagine, la glutamine, l’isophorone diamine, diaminodiphenylsulfone, l’hexaméthylène diamine, la m-xylendiamine et les polyétheramines telles que Jeffamine D-230, Jeffamine T-403 et leurs mélanges. [Claim 3] Hydrogel according to claims 1 or 2, in which the water-soluble di-, tri-, or polyamine is selected from lysine, arginine, asparagine, glutamine, isophorone diamine, diaminodiphenylsulfone, l ' hexamethylene diamine, m-xylendiamine and polyetheramines such as Jeffamine D-230, Jeffamine T-403 and mixtures thereof.
[Revendication 4] Hydrogel selon l’une des revendications précédentes, dans lequel le ratio en équivalent époxyde d’isosorbide monomère ou polymère hydrosoluble sur le nombre de fonctions N-H de l’amine hydrosoluble est compris entre 1 :5 et 5 :1, de préférence entre 1 :2 et 2 :1 et plus préférentiellement 1 :1.[Claim 4] Hydrogel according to one of the preceding claims, in which the ratio of epoxide equivalent of isosorbide monomer or polymer water-soluble on the number of NH functions of the water-soluble amine is between 1: 5 and 5: 1, preferably between 1: 2 and 2: 1 and more preferably 1: 1.
[Revendication 5] Hydrogel selon l’une des revendications précédentes, présentant un taux d’hydratation de 50 à 99 %. [Claim 5] Hydrogel according to one of the preceding claims, exhibiting a hydration level of 50 to 99%.
[Revendication 6] Hydrogel selon l’une des revendications précédentes, comprenant en outre un actif soluble dans l’eau, de préférence une molécule odorante, un actif cosmétique ou un actif pharmaceutique hydrosoluble et plus préférentiellement l’isosorbide.. [Claim 6] Hydrogel according to one of the preceding claims, further comprising an active soluble in water, preferably a scent molecule, a cosmetic active or a water-soluble pharmaceutical active and more preferably isosorbide.
[Revendication 7] Procédé de préparation d’un hydrogel tel que défini dans les revendications 1 à 6 comprenant les étapes suivantes : [Claim 7] A method of preparing a hydrogel as defined in claims 1 to 6 comprising the following steps:
1) Mélanger l’époxyde d’isosorbide monomère ou polymère hydrosoluble avec une amine hydrosoluble, 1) Mix the water-soluble monomer or polymer isosorbide epoxide with a water-soluble amine,
2) Ajouter au précédent mélange de l’eau, 2) Add to the previous mixture of water,
3) Mélanger jusqu’à obtenir un liquide translucide, et 3) Mix until you obtain a translucent liquid, and
4) Laisser réagir. 4) Let react.
[Revendication 8] Procédé de préparation d’un hydrogel selon la revendication 7, dans lequel l’étape 2) comprend l’ajout d’un actif. [Claim 8] A method of preparing a hydrogel according to claim 7, wherein step 2) comprises adding an active.
[Revendication 9] Utilisation d’un hydrogel tel que défini dans les revendications 1 à 6 dans le domaine médical, cosmétique, agricole, optique, dans le domaine du traitement de l’eau, des produits d’hygiène, dans la technologie de séparation ou dans l’énergie. [Claim 9] Use of a hydrogel as defined in claims 1 to 6 in the medical, cosmetic, agricultural, optical field, in the field of water treatment, hygiene products, in separation technology or in energy.
EP20824305.5A 2019-11-27 2020-11-26 Water-based hydrogel, and reaction product of isosorbide epoxide and amines Pending EP4065624A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1913342A FR3103380B1 (en) 2019-11-27 2019-11-27 Hydrogel based on water, and the reaction product of isosorbide epoxide and amines
PCT/FR2020/052182 WO2021105619A1 (en) 2019-11-27 2020-11-26 Water-based hydrogel, and reaction product of isosorbide epoxide and amines

Publications (1)

Publication Number Publication Date
EP4065624A1 true EP4065624A1 (en) 2022-10-05

Family

ID=69630500

Family Applications (1)

Application Number Title Priority Date Filing Date
EP20824305.5A Pending EP4065624A1 (en) 2019-11-27 2020-11-26 Water-based hydrogel, and reaction product of isosorbide epoxide and amines

Country Status (6)

Country Link
US (1) US20220403118A1 (en)
EP (1) EP4065624A1 (en)
JP (1) JP2023503358A (en)
KR (1) KR20220108774A (en)
FR (1) FR3103380B1 (en)
WO (1) WO2021105619A1 (en)

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7619056B2 (en) * 2006-06-02 2009-11-17 New Jersey Institute Of Technology Thermoset epoxy polymers from renewable resources
JP2009543902A (en) 2006-07-10 2009-12-10 メディパックス インコーポレイテッド Superelastic epoxy hydrogel
WO2013058778A1 (en) * 2010-11-01 2013-04-25 Nanoderm Sciences, Inc. Polymers and hydrogels
CN106474051B (en) * 2011-03-21 2022-07-08 博任达生化科技（上海）有限公司 Reverse temperature-sensitive reversible hydrogel composition
FR3016631B1 (en) 2014-01-21 2016-03-04 Roquette Freres PROCESS FOR PRODUCING GLYCIDYL ETHERS OF ISOHEXIDES PRODUCED THUS OBTAINED AND THEIR USES
US9605108B2 (en) * 2014-04-24 2017-03-28 New Jersey Institute Of Technology Isosorbide-derived epoxy resins and methods of making same

Also Published As

Publication number Publication date
WO2021105619A1 (en) 2021-06-03
FR3103380A1 (en) 2021-05-28
KR20220108774A (en) 2022-08-03
US20220403118A1 (en) 2022-12-22
FR3103380B1 (en) 2022-08-12
JP2023503358A (en) 2023-01-27

Similar Documents

Publication Publication Date Title
KR101884772B1 (en) Silicone compositions comprising a swollen silicone gel
JP5376543B2 (en) Polyion dendrimer and hydrogel comprising the same
CA2276711C (en) Antimicrobial polymers comprising quaternary ammonium groups, their use for making a material with antimicrobial properties and methods for preparing them
CN1426424A (en) Compound comprising crosslinked polyrotaxane
FR2465235A1 (en) CONTACT LENS PRODUCED FROM POLYSILOXANE POLYMERS AND POLYCYCLIC ACRYLIC OR METHACRYLIC ESTERS
FR2847166A1 (en) DOSAGE FORM COMPRISING CLOSED TAMSULOSIN PAGS, METHOD FOR PREPARING THE SAME, AND USE THEREOF
EP0377370A1 (en) Process for encapsulating particles by means of a thermoplastic silicon copolymer, and such particles
CH667008A5 (en) PROCESS FOR THE TREATMENT OF PHARMACEUTICAL DOSAGE FORMS.
FR3066116A1 (en) PROCESS FOR PREPARING BIODEGRADABLE CAPSULES AND CAPSULES OBTAINED
CA2596147A1 (en) Copolyhydroxyalkylglutamines which are functionalised with hydrophobic groups and applications thereof, such as in therapeutics
EP2408718A1 (en) Composition based on calcium hydroxide, method for the production thereof and use of same for treating water and mud
Yu et al. Materials established for enantioselective release of chiral compounds
EP3600642A1 (en) Method for preparing capsules with improved retention properties and capsules obtained therefrom
WO2021105619A1 (en) Water-based hydrogel, and reaction product of isosorbide epoxide and amines
Blelloch et al. Crystal engineering of molecular solids as temporary adhesives
EP0389386A1 (en) Polyester-polysiloxane block copolymer degradable by hydrolysis
FR2940064A1 (en) ANTI-TRANSPARENT AGENT COMPRISING COMPONENTS CAPABLE OF FORMING COVALENT BONDS BETWEEN THEM AND METHOD OF TREATING HUMAN TWO STEP TRANSPIRATION
EP0043317B1 (en) Process for the preparation of a polymer of the cross-linked polyurethane type having a tridimensional structure, product obtained by this process and its use as a swelling agent, especially therapeutically
FR3059665B1 (en) PROCESS FOR THE PREPARATION OF MICROCAPSULES AND MICROPARTICLES OF CONTROLLED SIZE
EP1487569B1 (en) Process for making biocompatible composite capsules
Johnson et al. Microfluidics assisted fabrication of microspheres by poly (2–hydroxyethyl methacrylate)-block-poly (l-histidine) hybrid materials and their utilization as potential drug encapsulants
CA2583783C (en) Complex containing mequitazine, a cyclodextrin and an interaction agent
WO2005051428A2 (en) Method for obtaining a thermoreversible gel with a controlled three-dimensional structure, and gel obtained
US9221994B2 (en) Aqueous based process to fabricate nanostructured block copolymer films
FR3132431A1 (en) COSMETIC GEL COMPOSITION COMPRISING PARTICLES

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20220603

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20231213