EP3094664A1 - Kombination aus kork/polyhydroxyurethanbindemittel und verfahren zur herstellung davon - Google Patents

Kombination aus kork/polyhydroxyurethanbindemittel und verfahren zur herstellung davon

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Publication number
EP3094664A1
EP3094664A1 EP15701493.7A EP15701493A EP3094664A1 EP 3094664 A1 EP3094664 A1 EP 3094664A1 EP 15701493 A EP15701493 A EP 15701493A EP 3094664 A1 EP3094664 A1 EP 3094664A1
Authority
EP
European Patent Office
Prior art keywords
compound
cork
groups
composition according
derivatives
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
EP15701493.7A
Other languages
English (en)
French (fr)
Inventor
Emilie DARROMAN
Clothilde Balbusquier
Sylvain Caillol
Bernard Boutevin
Rémi Auvergne
Christophe Loisel
Dominique Tourneix
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.)
Centre National de la Recherche Scientifique CNRS
Universite de Montpellier I
Ecole Nationale Superieure de Chimie de Montpellier ENSCM
Diam Bouchage SAS
Original Assignee
Centre National de la Recherche Scientifique CNRS
Universite Montpellier 2 Sciences et Techniques
Ecole Nationale Superieure de Chimie de Montpellier ENSCM
Diam Bouchage SAS
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 Centre National de la Recherche Scientifique CNRS, Universite Montpellier 2 Sciences et Techniques, Ecole Nationale Superieure de Chimie de Montpellier ENSCM, Diam Bouchage SAS filed Critical Centre National de la Recherche Scientifique CNRS
Publication of EP3094664A1 publication Critical patent/EP3094664A1/de
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G71/00—Macromolecular compounds obtained by reactions forming a ureide or urethane link, otherwise, than from isocyanate radicals in the main chain of the macromolecule
    • C08G71/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/007—Cork
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
    • B27N1/00—Pretreatment of moulding material

Definitions

  • the present invention relates to a composition
  • a composition comprising cork or a cork-based material and a binder which comprises at least one particular polyhydroxyurethane, its method of preparation, a process for producing a cork and the use of a polyhydroxyurethane as an adhesive for cork or a cork material.
  • Cork is a natural, impervious and light material, which comes from the bark of some species of oaks, such as cork oaks, which are typically found in the countries around the Mediterranean, Europe and North Africa.
  • Cork is particularly used in the manufacture of corks, which are used to plug containers such as bottles containing liquids for food, especially wine.
  • Cork is an elastic material, resilient, compressible and impermeable to liquids, having at the same time a gas permeability sufficient to allow an exchange necessary for the maturation of the bottled product, and having a high coefficient of friction.
  • cork is limited to a few areas of the world in which cork oak cultivation is profitable, and the production of natural cork scarcely balances needs.
  • This research led to the manufacture of agglomerated cork stoppers consisting of cork particles and a binder or glue which ensures the cohesion of the stopper. It has also been tried to manufacture fully synthetic plugs, especially based on polyethylene or other plastics.
  • the polyurethanes are usually formed from the reaction between a di-isocyanate and a compound having two functions with a mobile hydrogen, mainly hydroxyl groups, for example a diol.
  • a disadvantage of these polyurethanes is their mode of synthesis which involves the use of monomers comprising several highly reactive isocyanate functions which make them very dangerous or even toxic monomers.
  • the production of polyurethanes therefore presents numerous chemical risks and is dangerous for the operators. Many research studies have been carried out to implement less dangerous formulations.
  • non-highly toxic raw materials is intended to mean raw materials which are not carcinogenic-mutagenic-reprotoxic (or CMR) class 1 A, 1 B and 2 molecules.
  • the invention aims to satisfy this need by proposing a new composition comprising cork or a cork-based material, and a binder which comprises one or more polyhydroxyurethanes as defined below, the binder being preferably partially or completely biobased.
  • bio sourced is intended to mean a compound derived from biomass which has or has not undergone chemical treatment, and which is not classified CMR, classes 1A, 1B and 2. Examples of biomass include plant, tree, vine, fruit, vegetable or algae extracts.
  • the polyhydroxyurethanes result from the reaction between a compound having two or more amino functions and a compound having two or more cyclic carbonate functions with 5, 6 or 7 members, and do not use isocyanate compounds. These are sometimes also called NIPU ("Non Isocyanate Polyurethanes" or polyurethanes without isocyanate) due to the formation of a hydroxyl group (-OH) in the ⁇ position of the urethane function during the reaction.
  • NIPU Non Isocyanate Polyurethanes
  • composition according to the invention is especially intended for the manufacture of corks, in particular for still, effervescent or spirits wine bottles or aqueous solutions such as fruit juices, or oils.
  • Corks thus produced and containing at least a portion of agglomerated cork based on a binder, retain the advantages of natural cork, with physical characteristics that are close to or even greater and with an external appearance similar to that of natural cork.
  • these plugs do not have the drawbacks of known synthetic plugs, especially for their lack of elasticity, their low gas tightness over time and their external appearance different from natural cork.
  • composition can be applied to all the stoppers with at least one agglomerated part as is the case for champagne corks or sparkling wines, corks with one or more washers at one or both ends (1 + 1, 2 + 2, 0 + 2 or any other possible combination).
  • the composition may be obtained by molding process or by extrusion or by any thermal process for reacting the ingredients of the composition under the conditions of temperature, pressure and time adequate to the invention.
  • This composition according to the invention makes it possible to obtain a plug having both good mechanical, organoleptic and hydrophobicity properties.
  • a first object of the present invention is therefore a composition comprising cork or a cork-based material and a binder which comprises one or more polyhydroxyurethanes resulting from the mixture of one or more compounds (A) having two or more than two cyclocarbonate groups with one or more compounds (B) having two or more amino groups.
  • Another object is a composition
  • a composition comprising cork or a cork-based material, one or more compounds (A) having two or more cyclo-carbonate groups and one or more compounds (B) having two or more amino groups.
  • the compounds (A) and (B) are non-highly toxic, and preferably bio-sourced.
  • Another object of the invention is a process for the preparation of said composition.
  • Yet another object is a method of making stoppers using such a composition.
  • the invention still has a cap that can be obtained by the manufacturing process.
  • the composition comprises cork or a cork-based material and a binder which comprises one or more polyhydroxyurethanes resulting from the mixing of one or more compounds (A) having two or more cyclocarbonate groups with one or more compounds (B) having two or more amino groups.
  • the cork or the cork-based material that can be used in the invention is especially in the form of a flour, granules preferably having a particle size of 0.01 mm up to 8 mm, plates, washers cork from the casing of cork plates, preferably in the form of a flour.
  • the particle size can be measured for example by the sieve method, at room temperature (20-25 ° C).
  • the cork or cork-based material is preferably present in an amount ranging from 1 to 95% by weight, more preferably from 10 to 90% by weight, and still more preferably from 50 to 85% by weight relative to the total weight of the cork. composition.
  • the polyhydroxyurethanes (or PHU) used in the composition according to the invention may be partially or completely bio-sourced. They are prepared from raw materials preferably bio sourced as specified above, namely raw materials from biomass and not being classified CMR, classes 1A, 1B and 2.
  • the compound (A) having two or more cycloalkyl groups and the compound (B) having two or more amino groups have a functionality greater than or equal to 2, more preferably 2 to 5, so as to avoid the formation of linear PHUs.
  • the functionality of the compounds (A) and (B) must lead to crosslinking.
  • the cyclocarbonate groups have 5, 6 or 7 atoms.
  • reaction between at least one compound (A) having two or more cyclocarbonate groups and at least one compound (B) having two or more amino groups is amino-lysis. It can be represented for example by the following scheme, in the case where (A) has cyclo carbonate groups with 5 atoms:
  • R ', R "and R'” representing a linear or branched alkylene group, or arylene optionally comprising in the chain, one or more heteroatoms O, N and / or S.
  • This reaction gives molecules containing at least one urethane (or carbamate) bond and at least one hydroxyl group. Since the primary amine can open cyclocarbonate in two different ways, primary alcohols and / or secondary alcohols are formed. Urethanization can be performed in the presence of various organic, organometallic or mineral catalysts well known in the art.
  • This reaction may be carried out at a temperature of from -20 to 200 ° C, preferably from 50 to 150 ° C under atmospheric pressure.
  • Said polyhydroxyurethane (s) used in the composition according to the invention preferably contains 10 to 100% by weight of urethane groups and 0 to 90% by weight of groups resulting from the reaction of epoxy with an amine, these percentages being expressed relative to the weight of the polyhydroxyurethane.
  • the binder which comprises one or more polyhydroxyurethanes is preferably present in an amount ranging from 5 to 99% by weight, better still from 10 to 90% by weight, and still more preferably from 15 to 50% by weight relative to the total weight of the composition.
  • cork or cork-based material and the binder are preferably present in the composition according to the invention in a weight ratio of cork or cork-based material on a binder ranging from 0.01 to 20, better still from 0.1 to 10. .
  • the composition is free from isocyanate, that is to say that it comprises 0% by weight of isocyanate relative to the total weight of the composition.
  • isocyanate any compound including an -NCO- function.
  • the binder may further comprise at least one polyepoxide resulting from mixing one or more compounds (D) having two or more epoxy groups with one or more compounds (B) having two or more amino groups.
  • At least one polyepoxide is present in the binder, it (they) is (are) present (s) preferably in an amount ranging from 0 to 90% by weight, better still from 1 to 30% by weight relative to the total weight binder.
  • the polyepoxides optionally used in the composition according to the invention are preferably prepared from non-highly toxic raw materials, better derived from biomass.
  • Compounds (D) having two or more epoxy groups and compounds (B) having two or more amino groups that may be used will be described below in more detail.
  • reaction between at least one compound (D) comprising two or more epoxy groups and at least one compound (B) comprising two or more amino groups can be represented for example by the following scheme:
  • R 'i and R 2 denote, independently of one another, a divalent, saturated or unsaturated, linear or branched, or cycloaliphatic or aromatic, aliphatic hydrocarbon chain which may comprise at least one heteroatom such as O, N and S, and can be substituted.
  • This reaction may be carried out at a temperature of from -20 to 250 ° C, more preferably from 50 to 150 ° C, at atmospheric pressure.
  • This reaction can be carried out in the presence of a catalyst such as a tertiary amine such as triethylamine, or an aminophenol, or a catalyst well known in the art.
  • a catalyst such as a tertiary amine such as triethylamine, or an aminophenol, or a catalyst well known in the art.
  • composition according to the invention may furthermore comprise one or more organic additives, whether sourced or not, preferably biobased.
  • the additive (s) is (are) chosen from homopolymers or copolymers of which at least one of the monomers is chosen from vinylidene chloride or fluoride, vinyl chloride, metacrylonitrile, acrylonitrile, C 1 -C 5 alkyl methacrylate, such as methyl methacrylate, styrene and ethylene; cellulose polymers; latexes (emulsion of polymer particles) such as, for example, polyisoprene, ethylene / vinyl acetate, styrene / acrylic acid or styrene / butadiene latices; silicone oils; paraffins; natural waxes; porogenic agents; glass beads such as those sold by Poraver or those sold by 3M under the reference "bubble glass”; and their mixtures.
  • the additive (s) is (are) chosen from homopolymers or copolymers of which at least one of the monomers is chosen from vinylidene chloride or fluoride, vinyl chloride
  • homopolymers or copolymers having at least one particular monomer mention may especially be made of vinylidene chloride homopolymer, vinylidene chloride / vinylidene fluoride / vinyl chloride / acrylonitrile copolymers, and acrylonitrile / methyl methacrylate copolymers. acrylonitrile / methyl methacrylate / methacrylonitrile copolymers, styrene / acrylonitrile copolymers, styrene / ethylene-butylene / styrene copolymers (or SEBS) and homopolymers or copolymers of ethylene.
  • vinylidene chloride homopolymer vinylidene chloride / vinylidene fluoride / vinyl chloride / acrylonitrile copolymers
  • acrylonitrile / methyl methacrylate copolymers acrylonitrile / methyl methacrylate / methacrylon
  • the additives may be in the form of cellular structures, and more particularly in the form of particles having an average size of less than 500 ⁇ .
  • additives When one or more additives is or are present, their amount may vary from 0.1 to 20% by weight, better still from 1 to 10% by weight relative to the total weight of the composition.
  • the invention also relates to the composition comprising:
  • the compounds (A) having two or more cyclocarbonate groups may result from the transesterification or esterification of an ester or polycarboxylic acid, with glycerol carbonate or a carbonate with 6 or 7 atoms, or by chemical insertion of the C0 2 on a compound containing at least one cyclic ether group, and more particularly on a compound (D) containing two or more epoxy groups, or alternatively by adding a cyclocarbonate bearing double ethylenic functional groups.
  • the invention also relates to a method for preparing the composition according to the invention. It includes the following steps:
  • step (i) at least one compound (D) having two or more epoxy groups can also be introduced.
  • the compound (A) will be mixed with the compound (B) in excess, and then the compound (D) will be added.
  • the process according to the invention may further comprise a preliminary step (io) of preparing compound (A) having two or more cyclocarbonate groups: • by transesterification or esterification of an ester or polycarboxylic acid ( ⁇ '), with glycerol carbonate or a carbonate with 6 or 7 atoms; or
  • This step (i 0 ) can be done just before step (i).
  • R represents H or a C 1 -C 5 alkyl group, such as methyl and ethyl,
  • R “i denotes a saturated or unsaturated, linear or branched, or cycloaliphatic or aromatic aliphatic hydrocarbon chain, which may comprise at least one heteroatom such as O, N and S, and which may be substituted, and
  • x ' ranges from 2 to 6, and preferably from 2 to 4.
  • This reaction is made at a temperature between -20 and
  • esters or polycarboxylic acids ( ⁇ ') used in the (trans) esterification preferably comprise 2 or more carboxy groups, more preferably 2 to 6, more preferably 2 to 4 carboxy groups.
  • aromatic acids or esters such as:
  • R ' 3 denotes an alkylene group, preferably C 1 -C 20, preferably C 3 -C 5 cycloalkylene, preferably C 6 -C 18 aromatic, which may contain an oxygen, nitrogen or sulfur atom;
  • r represents an integer ranging from 2 to 20, where the tartaric and citric acids or esters
  • R '4 and R' 5 are each independently of one another, an alkylene group, preferably C1-20 cycloalkylene preferably C3-15, preferably aromatic C 6 -i8, may bear substituents such as alkyl, preferably C 1-5 , optionally having one or more heteroatoms such as O, N and / or S, and n is 1 to 50, more preferably 1 to 20,
  • o acid-graft copolymers such as poly (acid)
  • n 1 or 2.
  • polycarboxylic esters or acids used in the (trans) esterification are chosen from:
  • r represents an integer ranging from 2 to 20
  • R ' 4 and R' 5 each represent, independently of one another, an alkylene group preferably of C 1-20 , cycloalkylene preferably of C 3-15, aromatic preferably of Ce-is, which can carry substituents such as alkyl preferably C 1-5, optionally containing one or more heteroatoms such as O, N and / or S, n is 1 to 50, preferably 1 to 20, and
  • R represents H, a C 1 -C 2 alkyl group, such as a methyl or ethyl group.
  • Another process for preparing compounds (A) comprising two or more cyclo-carbonate groups is to insert CO2 in a compound containing at least two cyclic ether groups, and more particularly in a compound (D) containing two or more than two epoxy groups, preferably from 2 to 5, more preferably 2 or 3 epoxy groups.
  • this carbonation process can be carried out in dimethylformamide (DMF) at 80 ° C. under 12 bar of CO 2 for 15 hours.
  • DMF dimethylformamide
  • Compounds (D) containing two or more epoxy groups may themselves be prepared from a polyol comprising two or more hydroxy groups, preferably from 2 to 5 hydroxy groups, and epichlorohydrin, of epibromohydrin, or glycido 1, or also by the method of allylation and oxidation.
  • the reaction from an alcohol and epichlorohydrin, epibromohydrin or glycidol can be carried out at a temperature ranging from -20 to 150 ° C, preferably from 0 to 120 ° C.
  • polyols having two or more hydroxy groups which can be used in the invention are chosen from:
  • mononucleic aromatic alcohols such as:
  • o lignin derivatives selected from p-coumaryl alcohol, coniferyl alcohol and sinapyl alcohol
  • R 3 represents a divalent, saturated or unsaturated, linear or branched, or cycloaliphatic or aromatic, saturated or unsaturated hydrocarbon chain which may comprise at least one heteroatom such as O, N and S, and which may be substituted, and preferably represents an alkylene group preferably C 1 -C 20 , preferably cycloalkylene C3-15, preferably aromatic C-is, which may carry substituents such as alkyl preferably C 1-5 optionally comprising one or more heteroatoms such as O, N and / or S;
  • polynucleic aromatic alcohols such as:
  • PB polybutadienes
  • PI polyisoprenes
  • farnesene such as those of formula:
  • Me is methyl
  • 1 is an integer from 1 to 10
  • m is an integer from 1 to 3
  • aliphatic alcohols such as: the products obtained by oxidation of dimers and trimers of C36-54 fatty acids, such as:
  • n 1 to 1000
  • R 9 represents a C 1 -C 20 alkylene, preferably C 3-15 cycloalkylene, preferably C 6-18 alkylene group, which may carry substituents such as C 1 -C 5 alkyl, optionally containing one or more several heteroatoms like O, N and / or S, and
  • Rio is a diol, polyethylene glycol, polypropylene glycol, polybutylene glycol or oligobutadiene hydroxy telechelic such as those defined above,
  • R 7 and R '7 are each independently of one another, an alkylene group, preferably C1-20, preferably C3-15 cycloalkylene, preferably aromatic C 6 -i8, may carry substituents such preferably C1-5 alkyl, optionally containing one or more heteroatoms such as O, N and / or S.
  • n 1 and 1,000
  • epoxidized oils and their acid derivatives or epoxidized fatty esters such as epoxidized soybean oils, more particularly those of formula:
  • the compounds (B) used in the invention comprise two or more amino groups, preferably 2 to 10, more preferably 2 to 5 amino groups. They can be aromatic or aliphatic.
  • Compounds (B) having two or more amino groups can be obtained by a first allylation of aromatic or aliphatic alcohols as described above, or crotonization or methallylation, followed by a thio-ene reaction. on double bonds with an aminated thiol, for example, cysteamine hydrochloride, in the presence of a thermal or photochemical initiator.
  • the thermal initiator may be of azo type such as azobisisobutyronitrile (AIBN).
  • AIBN azobisisobutyronitrile
  • photochemical initiator By way of example of a photochemical initiator, mention may be made of 2-hydroxy-2-methyl-1-phenylpropanone as that sold under the trade name Darocur 1173 or bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide such as that sold under the trade name Irgacure 8 19.
  • R 4 denotes a linear C 1-5 alkylene group
  • R 4 denotes a linear or branched C 1-5 alkylene group, such as methylene and ethylene;
  • R 4 denotes a linear or branched C 1-5 alkylene group, such as methylene and ethylene;
  • R 4 denotes a linear or branched C 1-5 alkylene group, such as methylene and ethylene, 1 is an integer ranging from 1 to 10, m is an integer from 1 to 3, p is a number integer from 0 to 10, and q ranges from 0 to 1;
  • vanillin derivatives (or coniferyl alcohol) of formulas:
  • R 4 denotes a linear or branched C 1-5 alkylene group, such as methylene and ethylene;
  • tannin derivatives such as catechol of formula:
  • R 4 denotes a linear or branched C 1-5 alkylene group, such as methylene and ethylene.
  • R 5 x between 0 and 5
  • dimers and trimers of fatty acids modified to amines and amidoamines such as those sold by the company Croda, of formulas:
  • G NH 2 ; - L - R5 - NH 2
  • amidoamines such as those sold under the trade name Epikure by the company Momentive;
  • polyether amines such as that sold under the trade name Jeffamine by the company Huntsman
  • the compounds (B) comprising two or more preferred amino groups are chosen in particular from:
  • R 4 denotes a linear or branched C 1 -C 5 alkylene group, such as methylene and ethylene, 1 is an integer ranging from 1 to 10, m is an integer ranging from 1 to 3, p is a number integer from 0 to 10, and q ranges from 0 to 1;
  • dimers and trimers of fatty acids modified to amines and amidoamines such as those sold by the company Croda, of formulas:
  • G NH 2 ; -N- R 5 - NH 2
  • An object of the invention is the composition obtainable by the method as described above.
  • Another object of the invention is a method of manufacturing plugs implementing a composition according to the invention.
  • composition according to the invention can be used in the manufacture of a technical cap such as "1 + 1", “2 + 2", “0 + 2" and “0+ 1", or agglomerated or microagglomerated plugs.
  • 1 + 1 is meant a stopper whose body is made of agglomerated cork granules with an adhesive which will be within the scope of the invention at least one polyhydroxyurethane described above, while the two ends are each composed of a washer made of natural cork, said washers being obtained by casing a piece of cork whose thickness corresponds to that of the washers.
  • the casing consists in taking a piece of cork by means of a punch.
  • the "2 + 2" stopper consists of an agglomerated part and 2 end washers, while the “0 + 2" stoppers for Champagne or the “0+ 1” stoppers for effervescent do not include a washer. one end and 2 or 1 washer (s) at the other end, respectively.
  • composition according to the invention may, for example, be used in the process for manufacturing stoppers as described in application FR 2 672 002.
  • the stopper obtained from a composition according to the invention has physical properties at least equivalent to, or even greater than, those of a natural cork stopper and corks containing at least a portion of agglomerated cork based on a binder. .
  • the properties of such a plug are characterized by the absence of water absorption characterized by the measurement of imbibition as well as the mechanical properties of the plug.
  • the imbibition measurement is made by immersing plugs in boiling water for 15 minutes.
  • the imbibition measurement should be less than 20%, preferably 18% and even more preferably less than 15%.
  • the mechanical properties are characterized by the compressive force to compress it or by the force that the stopper returns to the neck of the bottle commonly called the springback.
  • plugs with a diameter of between 26 and 3 1 mm are characterized by the measurement of compression pressure. This measurement is done by compressing a stopper with a piston that moves at a speed of 10mm / min, with a diameter between 15 and 16 mm. The compression value is brought back to the cylindrical surface of the plug. This must be between 15 and 60 N / cm 2 and preferably between 25 and 60 N / cm 2 depending on the diameters of the plugs.
  • plugs with a diameter of between 20 and 25 mm are characterized by measuring the return force exerted by the plug after the plug has been compressed to a diameter of 15 to 16 mm, and then returned to a diameter between 18 to 21 mm and held for 3 minutes. The force obtained is returned to the cylindrical surface of the plug to obtain the springback.
  • the invention also relates to the use of a polyhydroxyurethane resulting from the mixing of one or more compounds (A) having two or more groups cyclocarbonates with one or more compounds (B) having two or more amino groups, as described above, as binder of cork or of a cork material.
  • This polyhydroxyurethane may be used in combination with at least one polyepoxide resulting from mixing one or more compounds (D) having two or more epoxy groups with one or more compounds (B) having two or more amino groups, as described above, as a binder for cork or a cork-based material.
  • the compound (A) is used in excess with respect to the compound (B).
  • Poly (glyco) polypropylene diglycidyl ether was reacted with CO 2 at a pressure of 12 bar in the presence of dimethylformamide (DMF) at 80 ° C for 15 hours.
  • DMF dimethylformamide
  • a compound (A) having a percentage of carbonate groups ranging from 25 to 100% by weight relative to the weight of the compound (A) is obtained.
  • PHU binders were prepared from the following ingredients shown in Table 1 below: Table 1
  • binders II were prepared by mixing 1 g of compound (A) and 0.46 g of compound (B); the addition of crosslinker can be up to 30% by weight relative to the carbonate. These binders were then crosslinked at 120 ° C. for 1 hour.
  • a plug was made by a molding process from cork flour and binder II having 25% urethane groups, prepared in Example 2.
  • the molding time is adapted according to the reactivity of the polyhydroxyurethane binder and can vary from 30 minutes to 2 hours.
  • the molding time is 2 hours in these examples.
  • the plugs obtained with the binder II prepared in Example 2 were then characterized with the methods for measuring the imbibition and the pressure in compression, indicated above.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP15701493.7A 2014-01-15 2015-01-15 Kombination aus kork/polyhydroxyurethanbindemittel und verfahren zur herstellung davon Pending EP3094664A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1450317A FR3016367B1 (fr) 2014-01-15 2014-01-15 Association liege/liant a base de polyhydroxyurethane et son procede de preparation
PCT/EP2015/050683 WO2015107113A1 (fr) 2014-01-15 2015-01-15 Association liège/liant à base de polyhydroxyuréthane et son procédé de préparation

Publications (1)

Publication Number Publication Date
EP3094664A1 true EP3094664A1 (de) 2016-11-23

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Country Link
EP (1) EP3094664A1 (de)
FR (1) FR3016367B1 (de)
WO (1) WO2015107113A1 (de)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MY190145A (en) * 2015-06-30 2022-03-30 Evonik Operations Gmbh Isocyanate-free reactive polyurethane compositions
FR3039146B1 (fr) * 2015-07-24 2021-11-19 Colas Sa Liants non bitumineux issus de composes phenoliques biosources et procedes de fabrication
FR3058419B1 (fr) * 2016-11-04 2023-03-10 Diam Bouchage Composition comprenant des granules de liege et une emulsion de substance hydrophobe, et bouchon prepare a partir de cette derniere
CN116323738A (zh) * 2020-06-04 2023-06-23 克莱姆森大学研究基金会 来自生物基多元醇的非异氰酸酯聚氨酯

Citations (1)

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