• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention relates to a composition comprising cork or a cork-based material and an epoxy binder prepared from non-highly toxic raw materials, preferably from biomass. In particular, the epoxide binder is synthesized from two particular reaction compounds (A) and (B), the compound (A) having at least two epoxy groups and the compound (B) having at least two amine groups. The invention also relates to the process for preparing said composition.
    公开号:FR3016368A1
    申请号:FR1450319
    申请日:2014-01-15
    公开日:2015-07-17
    发明作者:Emilie Darroman；Clothilde Balbusquier；Sylvain Caillol；Bernard Boutevin；Remi Auvergne；Christophe Loisel；Dominique Tourneix
    申请人:Centre National de la Recherche Scientifique CNRS；Universite de Montpellier II；Ecole Nationale Superieure de Chimie de Montpellier ENSCM；Diam Bouchage SAS；
    IPC主号:
    专利说明:

    [0001] The present invention relates to a composition comprising cork or a cork-based material and a binder which comprises at least one polyepoxide, its method of preparation, a manufacturing method. a plug and the use of polymers synthesized by opening epoxy functions as adhesives for cork or cork-based material.
    [0002] 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 serve 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. Much research has been conducted to try to develop compositions whose properties are similar to those of natural cork and which can replace it especially for the manufacture of corks, for example corks for closing wine bottles. In fact, cork harvesting is limited to a few areas of the world in which cork oak cultivation is profitable, and the production of natural cork barely 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.
    [0003] It has also been tried to manufacture fully synthetic plugs, especially based on polyethylene or other plastics. However, all caps, their known manufacturing processes and their composition have drawbacks and do not use only natural raw materials. There is therefore a need to produce a composition obtained from non-highly toxic natural raw materials, having both good mechanical and organoleptic properties. For the purposes of the present invention, the term "non-highly toxic raw materials" means raw materials which are not classifiable carcinogenic-mutagenic-repellent (or CMR) molecules, classes 1A, 1B and 2. The invention aims to satisfy this need by proposing a new composition comprising cork or a cork-based material, and a binder comprising one or more polyepoxides as defined below, this binder being partially or totally bio sourced. For the purposes of the present invention, the term "biosourced" is intended to mean a compound derived from biomass which has or has not undergone chemical treatment, and which is not classified as CMR, classes 1A, 1B and 2. As examples of biomass, there may be mentioned extracts of plants, trees, vines, fruits, vegetables or algae. The composition according to the invention is especially intended for the manufacture of corks, in particular for bottles of still, sparkling or spirits wines 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. In addition, the plugs do not have the disadvantages of known synthetic plugs, especially for their lack of elasticity, their low gas tightness over time and their appearance different from natural cork. Thus, the 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 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.
    [0004] 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 polyepoxides resulting from the mixture of one or more compounds (A) having two or more groups epoxies with one or more compounds (B) having two or more amine groups. Another object is a composition comprising cork or a cork-based material, one or more compounds (A) having two or more epoxy groups and one or more compounds (B) having two or more amine groups.
    [0005] The invention further relates to a process for preparing said composition. Yet another object is a method of making stoppers using such a composition. The invention also relates to a plug that can be obtained by the manufacturing process. Other characteristics and advantages of the invention will emerge more clearly on reading the description and examples which follow.
    [0006] In what follows, and unless otherwise indicated, the boundaries of a domain of values are included in this field, especially in the expressions "between" and "from ... to".
    [0007] Moreover, the expression "at least one" used in the present description is equivalent to the expression "one or more". According to the invention, the composition comprises cork or a cork-based material and a binder comprising one or more polyepoxides resulting from the mixture of one or more compounds (A) having two or more epoxide groups with one or more compounds (B) having two or more amine groups. The cork or the cork-based material that can be used in the invention is in particular 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 polyepoxides used in the composition according to the invention are partially or totally biobased. They are prepared from biobased raw materials as specified above, namely raw materials derived from biomass and not classified CMR, classes 1A, 1B and 2. The reaction between at least one compound (A) comprising at least two epoxy groups and at least one compound (B) having at least two amine groups can be represented for example by the following scheme, in the case where (B) has primary amine groups: H2N R2 X and y> 0 HO compound Ri (A) compound (B) in which x varies from 1 to 4 and y ranges from 1 to 9, and R1 and R2 denote, independently of each other, a divalent, saturated or unsaturated, linear or branched aliphatic hydrocarbon chain; or cycloaliphatic or aromatic, may comprise at least one heteroatom such as O, N and S, and may be substituted. Compounds (A) having two or more epoxy groups and compounds (B) having two or more amine groups that can be used will be described in more detail below. 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 aminophenol, or a catalyst well known in the art. The binder which comprises one or more polyepoxides resulting from the admixture of one or more compounds (A) having two or more epoxide groups with one or more compounds (B) having two or more amine groups, 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. The cork or cork-based material and the epoxy binder are preferably present in the composition according to the invention in a weight ratio cork or cork-based material on epoxy binder ranging from 0.01 to 20, better still 0.1 to 10.
    [0008] In particular, the composition is free of bisphenol A, that is to say that it comprises 0% by weight of bisphenol A relative to the total weight of the composition. The composition according to the invention may further comprise one or more biobased additives or not, preferably biobased. This additive or these additives can in particular contribute to the homogeneity of the structure. They can also have hydrophobic properties. Preferably, 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, methacrylonitrile, acrylonitrile, C1-5 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. As examples of 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 / ethylenebutylene / styrene copolymers (or SEBS) and homopolymers or copolymers of ethylene.
    [0009] In a preferred embodiment, 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 μm.
    [0010] 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: - cork or a material based on cork, - at least one compound (A) comprising two or more epoxy groups, and - at least one compound (B) comprising two or more than two amine groups, and - optionally at least one additive as described above, preferably biosourced. Preferably, the compound (A) having at least two epoxy groups can be prepared from a polyol comprising two or more hydroxy groups, preferably from 2 to 5 hydroxy groups and epichlorohydrin, epibromohydrin or glycidol, or also by the method of allylation and oxidation. The invention also relates to a process for preparing the composition according to the invention. It comprises the following steps: (i) mixing cork or cork material with at least one compound (A) having two or more epoxy groups and at least one compound (B) having two or more groups amines, at a temperature ranging from 0 to 150 ° C, preferably from 10 to 50 ° C, under atmospheric pressure, for a time ranging from 5 to 120 minutes, preferably from 10 to 60 minutes; and (ii) heating at a temperature of from -20 to 200 ° C, preferably from 50 to 150 ° C, at atmospheric pressure, for a period of from 15 to 150 minutes, preferably from 30 to 120 minutes. The process according to the invention may comprise a further prior step (io) of preparing compound (A) having at least two epoxy groups from a polyol comprising two or more hydroxy groups, preferably from 2 to 5 hydroxy groups and epichlorohydrin, epibromohydrin or glycidol, or also by the method of allylation and oxidation.
    [0011] 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. This step (io) can be done just before step (i).
    [0012] Examples of polyols comprising two or more hydroxyl groups that may be used in the invention are chosen from: mononuclear aromatic alcohols such as: o resorcinol HO OH o hydroquinone o phloroglucinol OH HO OH HO o vanillin and its derivatives, wherein n = 0, 2, 4 or 6 o lignin derivatives selected from p-coumaryl alcohol, coniferyl alcohol and The derivatives of coumarin (Hoy x = 01 o gallic acid HO OH o the aw diphenols HO OH in which R3 represents a divalent, saturated or unsaturated, linear or branched aliphatic hydrocarbon chain or cycloaliphatic or aromatic, which may comprise at least one heteroatom such as O, N and S, and which may be substituted, and preferably represents a preferably C 1 -C 20 alkylene, preferably C 3 -C 15 cycloalkylene, preferentially aromatic C6-18, which may have substituents such as C1-C5alkyl optionally containing one or more heteroatoms such as O, N and / or S; polynucleic aromatic alcohols, such as: o oligo-styrol, the monomer of which corresponds to the formula: ## STR1 ## cardanol phenol, dinucleic aromatic alcohols, such as: vanillin dimers, where: ## STR1 ## , 1,2,3 x = 0,1,2,3 o the phenol products of oils and other polyenes such as polybutadienes (PB), polyisoprenes (PI), and farnesene, such as those of formula: o In which Me denotes the methyl group, 1 is an integer ranging from 1 to 10, m is an integer ranging from 1 to 3, and p is an integer ranging from 1 to 10, subject to that 1 + 3m + p = 17; aliphatic alcohols such as the products obtained by oxidation of dimers and trimers of C36-54 fatty acids, such as: HO HO HO such as those sold by Croda, sugars, (oligo) glycerols and isosorbides of formulas OH HO OH HO diols, polyethylene glycols, polypropylene glycols, polybutylene glycols and telechelic hydroxy oligobutadienes, such as those of formulas: ## STR2 ## with n ranging from 1 to 1000, the polyesters-diols of formula: ## STR2 ## in which R 9 represents a C 1-20 alkylene group, preferably a C 3 -C 15 cycloalkylene group, preferably C 6-18 aromatic, which may have substituents such as C 1-5 alkyl, optionally having one or more heteroatoms such as O, N and / or S, and R 10 is a diol, polyethylene glycol, polypropylene glycol, polybutylene glycol or oligobutadiene hydroxy telechelic 15 such as those defined above essus, polycarbonates-diols of formula> OH-HO. In which x is from 1 to 1000, R 7 and R 7 each independently represent a C 1-20 alkylene group, preferably a C 3 -C 15 cycloalkylene group. preferably C 6-18 aromatic, which may carry substituents such as C 1 -C 5 alkyl optionally containing one or more heteroatoms such as O, N and / or S. As examples of compounds (A) containing two or more more than two epoxy groups, which may be commercial, may be mentioned in particular: the vanillin derivatives of formulas (I) and (II) / (I) 1 "---, c) I (II) the derivative gallic acid of formula (III): epoxidized phloroglucinol polyepoxidized cardanol of formula: such as that sold under the trade name NC-514 by the company Cardolite, polypropylene glycol diglycidyl ether with n between 1 and 1000, such as that sold under the reference DER® 732E by the company 15 DOW, the epoxidized oils and the its acid derivatives or epoxidized fatty esters such as epoxidized soybean oils, more particularly those of formula: pMe in which Me designates the methyl group, 1 is an integer ranging from 1 to 10, m is an integer ranging from 1 to 3, and p is an integer from 1 to 10, provided that 1 + 3m + p = 17. By way of example of such oils, there may be mentioned the one sold under the trademark "Vikoflex" by Arkema; and epoxidized tea tannins and epoxidized catechins. The compounds (B) used in the invention comprise two or more amine groups, preferably from two to ten, more preferably from 2 to 5. They may be aromatic or aliphatic. Compounds (B) having two or more amine groups can be obtained by a first allylation of aliphatic or aromatic alcohols as described above, or crotonization or methallylation, followed by a thiol-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 can be of the azo type such as azobi if sobutyronitrile (AIBN). By way of example of a photochemical initiator, mention may be made of 2-hydroxy-2-methyl-1-phenylpropan-1-one such 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 819. By way of examples of compounds (B) comprising two or more amine groups, there may be mentioned in particular: the derivatives of oils of formula: in where R4 denotes a linear or branched C1-C5 alkylene group, such as methylene and ethylene, Me denotes the methyl group, 1 is an integer ranging from 1 to 10, m is an integer ranging from 1 to 3, and p is an integer from 1 to 10, provided that 1 + 3m + p = 17; polybutadiene derivatives bearing -S-R 4 -NH 2 groups, R 4 denoting a linear or branched C 1 -C 5 alkylene group, such as methylene and ethylene; allylamine derivatives of formula: H2N-R NH2 4 R4 denoting a C1-C5 alkylene, methylene and ethylene group; trimethylolpropane derivatives of formula: ## STR2 ## denoting a linear or branched C 1 -C 5 alkylene group, such as methylene and ethylene; the pentaerythritol derivatives of formula: ## STR2 ## in which R 1 is methyl or branched; , such as with 0 <x <2, and R4 denoting a linear or branched C1-C5 alkylene group, such as methylene and ethylene; - cardanol derivatives of the formula: HO / SR4 ---- NH2) as R4 linear or NH 2 wherein R 4 is a branched C 1-5 alkylene group, such as methylene and ethylene, 1 is an integer from 1 to 10, m is an integer of 1 to 3, p is an integer ranging from 0 to 10, and q ranges from 0 to 1; the allyl cardanol derivatives of formula: embedded image in which 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 a whole number; ranging from 1 to 3, p is an integer from 0 to 10, and q ranges from 0 to 1; allyl vanillin derivatives of formulas: wherein R 4 denotes a linear or branched C 1 -C 5 alkylene group, such as methylene and ethylene; the allylated gallic acid derivative of formula: ## STR5 ## with 0 <x <2, and R 4 denoting a linear or branched C 1 -C 5 alkylene group; such as methylene and ethylene; allylated tannin derivatives, such as catechine of formula: I-12N, wherein R4 is a linear or branched C1-C5 alkylene group such as methylene and ethylene.
    [0013] As examples of other compounds (B) which can be used in the invention and which are commercial or which naturally have amino compounds, there may be mentioned in particular: a phenalkamine of formula: OS, R, NH 2 H 2 N 'SO R4 n = 0, 2, 4 or 6 R5: -ECH2-CH2-N) -CH2-CH2- x between 0 and 5 FII x -ECH2 including between 2 and 12 Y such as, for example, that sold under the trade name NX-5454 by the company Cardolite; the furan derivative of formula: NI-12 - polylysine; chitosan and its derivative oligomers; dimers and trimers of fatty acids modified to amines and amidoamines, such as those sold by the company Croda, of formulas: ## STR2 ## -N-R 5 -NH 2 H and R 5 being defined as above; amidoamines such as those sold under the trade name Epikure by the company Momentive; polyethylenesulfines H H2N N with n ranging from 1 to 10, such as tetraethylenepentamine (TEPA, n = 3) and triethylenetetramine (TETA, n = 2); polyether amines such as that sold under the trade name Jeffamine by Huntsman H N.V..0 CH3 with x, y, z and n ranging from 1 to 1000; and the diamines of formula: H 2 N-1, A, NH 2 n = 3 to 12 Compounds (B) containing two or more preferred amine groups are in particular chosen from: cardanol derivatives of formula H 0 2 Ci R 4 NH 2 in wherein R4 denotes a linear or branched C1-5 alkylene group, such as methylene and ethylene, 1 is an integer from 1 to 10, m is an integer from 1 to 3, p is an integer ranging from 0 to 10, and q is from 0 to 1 allyl cardanol derivatives of the formula: ## STR2 ## ## STR2 ## 2) NH 2 2N 'o R 4 NH 2 in which 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 1-3, p is an integer from 0 to 10, and q ranges from 0 to 1; the phenalkamines sold by the company Cardolite, of formula OH, R5, IH, FI ## STR5 ## between 0 and 5 x - (C1-12- ± including between 2 and 12 Y dimers and trimers of fatty acid modified amines and amidoamines such as those sold by the company Croda, of formulas: 0 G = NH; H R5 defined as above and polypropylene glycol diamine or triamine such as that sold under the trade name Jeffamine as Jeffamine D400 or Jeffamine T403 by the company Huntsman, represented by the formulas: Fi2N); - NH2 r An object of the invention The invention relates to the composition obtainable by the process as described above. The subject of the invention is also a process for the manufacture of plugs using a composition according to the invention. For example, the composition according to the invention can be used in the manufacture of a technical stopper such as "1 + 1", "2 + 2", "0 + 2" and "0 + 1", or agglomerated or microagglomerated stoppers. By "1 + 1" is meant a plug whose body consists of agglomerated cork granules with an adhesive which will be within the scope of the invention at least one polyepoxide described above, while both ends are composed each of a washer 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 cap "2 + 2" consists of an agglomerated part and with two washers at the ends, while the caps "0 + 2" for champagne or caps "0 + 1" for effervescent do not include washer at one end and 2 or 1 washer (s) at the other end, respectively. The composition according to the invention may, for example, be used in the process for manufacturing stoppers as described in application FR 2 672 002. Still another object is a stopper capable of being obtained by the manufacturing process.
    [0014] 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 that of corks containing at least a portion of agglomerated cork based on binder . The properties of such a plug are characterized by the absence of water absorption characterized by the measurement of imbibition and the mechanical properties of the plug. The imbibition measurement is made by immersing corks in boiling water for 15 min. The imbibition measurement must be less than 20%, preferably 18% and even better 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.
    [0015] As an indication, plugs with a diameter of between 26 and 31 mm are characterized by the measurement of compression pressure. This measurement is done by compressing a plug with a piston which moves at a speed of 10 mm / min, to a diameter of 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 according to the diameters of the plugs. As an indication, plugs of diameter between 20 and 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, then returned to a diameter of 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. This must be understood for the still wine corks (diameter of the order of 24 mm) between 0.8 and 5 N / cm2, better ranging from 1.5 to 4.5 N and preferably 2 to 4 N. L Another subject of the invention is the use of a polyepoxide obtained from at least one compound (A) comprising at least two epoxy groups and from at least one compound (B) comprising at least two amine groups as described above, as a binder for cork or a cork-based material. The following examples are given purely by way of illustration of the present invention. EXAMPLES Example 1 Preparation of Polyepoxide Binders Polyepoxide binders were prepared from the following ingredients listed in Table 1 below: Table 1 Binder Compound (A) Compound (B) Crosslinking Agent I Cardanol Phenalkamine Triglycidyl Ether Trimethylolpropane Triglycidyl Ether Polyepoxide Trimethylolpropane II Cardanol Polyepoxide Polyepoxide Glycol diamine Mixtures of a compound (A) having at least two epoxy groups and a compound (B) having at least two amine groups as indicated in Table 1 were used with 0, 10, 20 or 30% by weight of crosslinking agent relative to the weight of the compound (A). The proportions are variable according to the compounds used and satisfy the following formula weight (amine) = AHEW / EEW * weight (epoxy) in which AHEW is the weight of equivalent amino hydrogen (Amine Hydrogen Equivalent Weight) and EEW is the epoxy equivalent weight (Epoxy Equivalent Weight). The binders without cork flour were then characterized using the methods given below.
    [0016] Thermal and mechanical analyzes were performed on the polyepoxide binders obtained. For the thermogravimetric analysis, ten milligrams of binder were dynamically tested under nitrogen at 10 ° C. For the glass transition measurement, a differential scanning calorimetry (DSC) analysis was carried out with a dynamic program. 20 ° C / min under nitrogen flow For the mechanical analyzes, a deformation was applied to the sample at 3 ° C / min under 1 Hz The results are as follows: a mass loss temperature of 5% between 240 C. and 300 ° C., a glass transition temperature of between -40 ° C. and 40 ° C., a mechanical transition temperature of between -40 ° C. and 40 ° C., and an elastic modulus of between 1 and 4 MPa; glassy module between 1500 MPa and 2500 MPa, and a crosslinking density of between 200 and 500 mol / m 3, Example 2 A plug was manufactured using a molding process from cork flour and epoxy binder. 70% in p oids, relative to the weight of the mixture, cork flour having a particle size ranging from 0.25 to 1.5 mm, and 30% by weight, relative to the weight of the mixture, of an epoxy binder prepared in the Example 1, in a tube which was closed and put in an oven at a temperature of 120 ° C. The molding time is adapted according to the reactivity of the epoxy binder and can vary from 30 minutes to 2 hours. In particular, the molding time is 1.5 hours in these examples.
    [0017] Compact caps that do not crumble on demolding were obtained. The plugs obtained with the various binders were then characterized with the methods described above. The results are summarized in Table 2 below.
    [0018] Table 2 Binder Amount of agent Volume density with plug (g / din3)% Imbibition Crosslinking pressure compression (% by weight) (N / cm2) 54 I 10% 330 11% I 20% 330 12% 53 I 30% 330 11 Example 3 Corks were made in the same manner as in Example 2, except that 50% by weight of the mixture of polyepoxide binder prepared in Example 2 was used. Example 1
    [0019] The molding conditions are the same. Compact caps that do not crumble on demolding were obtained. The composites obtained with the different binders were then characterized.
    [0020] The density of each stopper, the imbibition rate and the compressive strength were measured according to the protocols mentioned in Example 2. The results are summarized in Table 3 below. Table 3 Binder Amount of agent Density e% Imbibition Crosslinking pressure plug (g / dm) compression (% wt) (N / cm2) I 0% 330 13% 32 I 30% 330 12% 49 II 0% 330 11% EXAMPLE 4 In this example, a binder III prepared from polypropylene glycol diglycidyl ether and a phenalkamine was used, with 30% by weight of trimethylolpropane triglycidyl ether as crosslinking agent, based on the weight of the polypropylene glycol diglycidyl ether, and an alveolar additive of synthetic origin. 64% by weight, relative to the weight of the mixture, of cork flour having a particle size ranging from 0.5 to 3 mm, 30% by weight, relative to the weight of the mixture, of the binder III prepared in Example 1 and 6% of the additive. Corks were made in the same manner as in Example 2, with the exception of tubes in which the mixture was put. A machine having molds containing several tubes was used. These were filled with the mixture and then closed after compression and the mold was put in a first oven at 200 ° C for 30 minutes and then at 80 ° C for 20 minutes. Compact caps that do not crumble on demolding were obtained. The composites obtained with the binder were then characterized.
    [0021] The results are summarized in Table 4 below. Table 4 Density% Pressure compression plug (g / dm3) Imbibition (N / cm2) 252 9.18% 3625
    权利要求:
    Claims (19)
    [0001]
    REVENDICATIONS1. A composition comprising cork or a cork material and a binder which comprises one or more polyepoxides resulting from the admixture of one or more compounds (A) having two or more epoxide groups with one or more compounds (B) comprising two or more amine groups.
    [0002]
    2. Composition according to claim 1, characterized in that it contains from 1 to 95% by weight, preferably from 10 to 90% by weight, of cork or a cork-based material, relative to the total weight of the product. composition.
    [0003]
    3. Composition according to claim 1 or 2, characterized in that the (s) polyepoxides are prepared from organic sourced raw materials.
    [0004]
    4. Composition according to any one of the preceding claims, characterized in that it contains from 5 to 99% by weight, preferably from 10 to 90% by weight, of binder which comprises one or more polyepoxides, relative to the weight total of the composition.
    [0005]
    5. Composition according to any one of the preceding claims, characterized in that the weight ratio cork or cork-based material on binder which comprises one or more polyepoxides ranges from 0.01 to 20, more preferably from 0.1 to 10.
    [0006]
    6. Composition according to any one of the preceding claims, characterized in that it is free of bisphenol A.
    [0007]
    A composition comprising: - cork or a cork-based material, - at least one compound (A) having two or more epoxy groups, and - at least one compound (B) having two or more amine groups .
    [0008]
    8. Composition according to any one of the preceding claims, characterized in that the compound (A) comprising at least two epoxy groups is prepared from a polyol comprising two or more hydroxyl groups, and epichlorohydrin, epibromohydrin or glycidol, or by the method of allylation and oxidation.
    [0009]
    9. Composition according to any one of the preceding claims, characterized in that it comprises one or more additives, preferably biosourcés.
    [0010]
    10. Composition according to claim 9, characterized in that 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, metacrylonitrile, acrylonitrile, C1-5 alkyl methacrylate, styrene and ethylene; cellulose polymers; latexes; silicone oils; paraffins; natural waxes; porogenic agents; glass beads and mixtures thereof.
    [0011]
    11. Composition according to claim 9 or 10, characterized in that the additive (s) is (are) present in an amount ranging from 0.1 to 20% by weight, better still from 1 to 10% by weight. weight relative to the total weight of the composition.
    [0012]
    12. Composition according to claim 8, characterized in that the polyols are chosen from mononucleic aromatic alcohols, dinucleic aromatic alcohols, polynucleic aromatic alcohols and aliphatic alcohols.
    [0013]
    13. Composition according to any one of claims 1 to 7 and 9 to 11, characterized in that the compounds (A) containing two or more epoxy groups are chosen from vanillin derivatives of formulas (I) and, (II) ## STR16 ## the gallic acid derivative of formula (III) epoxidized phloroglucinol and polyepoxidized cardanol of formula: polypropylene glycol diglycidyl ether oNo with n between 1 and 1000, epoxidized oils and their acid derivatives or epoxidized fatty esters and epoxidized tea tannins and epoxidized catechin.
    [0014]
    14. Composition according to any one of claims 1 to 13, characterized in that the compounds (B) comprising two or more amine groups are chosen from: the oil derivatives of formula: Nii 2 5 -R 4 in which R 4 denotes a linear or branched C 1 -C 5 alkylene group, 1-12> R 4 such as methylene and ethylene, Me denotes the methyl group, 1 is an integer ranging from 1 to 10, m is an integer ranging from 1 to 3; , and p is an integer from 1 to 10, with the proviso that 1 + 3m + p --- 17; polybutadiene derivatives bearing -S-114-NH2 groups, R4 denoting a linear or branched C1-5 alkylene group, such as methylene and ethylene; allylamine derivatives of formula: H 2 N -R 4 R 4 denoting a linear or branched C 1 -C 5 alkylene group, such as methylene and ethylene; trimethylolpropane derivatives of formula R4 denoting a linear or branched C 1-5 alkylene group, such as methylene and ethylene; pentaerythritol derivatives of formula: (HO-Cl-12) -C - (- CH2-O-C3H6-S-R4 -N112) with with 0 <x <2, and R4 denoting a C1-alkylene group. 5, linear or branched, such as methylene and ethylene; the cardanol derivatives of ## STR2 ## wherein 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 4. 10, m is an integer from 1 to 3, p is an integer from 0 to 10, and q ranges from 0 to 1; the allyl cardanol derivatives of formula ti2N-R4 S, R4-NH2) qR4 1 NH2 in which R4 denotes a linear or branched C1-5 alkylene group, such as methylene and ethylene, 1 is an integer ranging from 1 at 10, m is an integer from 1 to 3, p is an integer from 0 to 10, and q ranges from 0 to 1; allylated vanillin derivatives of formulas: ## STR2 ## R4 denotes a C1-5 alkylene group, linear or branched, such as methylene and ethylene; The allylated gallic acid derivative of the formula: NH 2 R 4 O 3 O 3 H 6 -S-R 4 -NH 2 3-x (Ho x with 0 <x <2, and R 4 denoting a linear or branched C 1 -C 5 alkylene group, such as methylene and ethylene, allylated tannin derivatives, such as catechol of the formula: ## STR2 ## Wherein R4 is a linear or branched C 1-5 alkylene group, such as methylene and ethylene; a phenalkamine of formula: ## STR5 # furan of formula: H2N NH2 polylysine; chitosan derivatives and their oligomers modified fatty acid dimers and trimers to amines and amidoamines of the formulas: ## STR2 ## N -R5-NH2 -and R5 denoting - (CH2-CH2-NH) x-CH2-CH2- with x ranging from 0 to 5, - (CH2) y- with y being between 2 and 12, or amidoamines; NH2 polyethyleneimines Fi2N with n ranging from 1 to 10; the polyether-amines H 2 N H 2 N C H 3 CH 3 with x, y, z and n ranging from 1 to 1000; and diamines of the formula H2N., ", NH2" n = 3 to 12
    [0015]
    15. Process for the preparation of the composition according to any one of the preceding claims, characterized in that it comprises the following steps: (i) mixing the cork or the cork-based material with at least one compound (A) comprising two or more epoxy groups and at least one compound (B) having two or more amine groups, at a temperature ranging from 0 to 150 ° C, preferably from 10 to 50 ° C, under atmospheric pressure, for a duration ranging from 5 to. 120 minutes, and (ii) heating at -20 to 200 ° C, preferably 50 to 150 ° C, at atmospheric pressure, for a period of from 15 to 150 minutes.
    [0016]
    16. The method of claim 15, characterized in that it comprises a further prior step (4) of preparing the compound (A) comprising at least two epoxy groups from a polyol comprising two or more hydroxyl groups and epichlorohydrin, epibromohydrin or glycidol, or by the method of allylation and oxidation.
    [0017]
    17. Composition characterized in that it is obtainable by the method according to any one of claims 15 to 16. 34 CH3 H2 NNN 0 (CHI (CH2). 0 '' '' NH2
    [0018]
    18. A method of manufacturing a stopper comprising the process for preparing the composition according to any one of claims 15 to 16.
    [0019]
    19. Use of the polyepoxides resulting from the blending of one or more compounds (A) having two or more epoxy groups and one or more compounds (B) having two or more amine groups, as a cork binder or of a cork-based material.
    类似技术:
    公开号 | 公开日 | 专利标题
    EP3094699B1|2019-02-06|Combination of cork / polyepoxide binder and method for manufacturing same
    CN100998424B|2010-12-15|Method for cooking fish with distillers&#39; grains
    WO2015107113A1|2015-07-23|Combination of cork / polyhydroxyurethane binder and method for manufacturing same
    CN104974683B|2018-10-26|The preparation method of adhesive is blended in a kind of konjaku flour-chitosan-PVA
    EA200700696A1|2007-10-26|POLYETHYLENE COMPOSITION FOR CAPS AND COVERS MADE BY MOLDING UNDER PRESSURE
    US9975841B2|2018-05-22|Large molecule and polymer flame retardants
    Zhu et al.2016|Isolation and analysis of four constituents from barks and leaves of Eucommia ulmoides Oliver by a multi-step process
    CN103989224B|2015-08-26|Gold hesperidium aurantium vinegar and golden hesperidium aurantium vinegar beverage production technology
    CN104760751B|2017-01-25|Artificial ceramic red wine cork and preparation method thereof
    WO2008062918A1|2008-05-29|Production method of coating mixture of uv paints comprising urushi lacquer, coating mixture of uv paints produced by thereof, and products produced by production method using coating mixture of uv paints
    JP4892727B2|2012-03-07|Enzymatic cross-linking reaction of macromolecular tannins
    CN109293959B|2021-07-30|Tea-residue-modified oxidized cellulose composite membrane and preparation method and application thereof
    CN1970722B|2010-09-29|Supercritical CO2 extraction method for aromatic matter in brewed spirit solid
    CN101429472B|2012-03-21|Method for producing coconut wine
    CN111763151B|2021-11-30|Preparation method of cardanol modified polyamine curing agent with high corrosion resistance
    CN108124727B|2020-02-07|Lac waste residue culture medium for soilless culture and preparation method thereof
    CN106189964B|2019-06-18|A kind of preparation method of bamboo liquefied substance base flame-retarding adhesive
    CN104194015A|2014-12-10|Preparation method of soybean protein/sodium alginate cross-linked membrane for food packaging
    JP2019089732A|2019-06-13|Agent, method for use thereof and production method
    CN105690515B|2018-02-16|Tea Polyphenols suppresses the purposes of Coriolus and gloeophyllum trabeum
    KR101813050B1|2017-12-28|A method for producing of plum wine containing reduced ethyl carbamate
    US20180127399A1|2018-05-10|Biosourced compound having epoxide functions, method for the synthesis of such a compound, and use thereof for producing epoxy resin
    WO2021089953A1|2021-05-14|Epoxy resin comprising an isosorbide epoxide
    WO2021089954A1|2021-05-14|Epoxide resin composition comprising an isosorbide epoxide and use thereof for stabilizing a fibrous or porous material
    CN109943239B|2021-02-19|Preparation method of nontoxic tissue slice mounting adhesive
    同族专利:
    公开号 | 公开日
    WO2015107114A1|2015-07-23|
    ES2719554T3|2019-07-11|
    EP3094699B1|2019-02-06|
    PT3094699T|2019-03-14|
    EP3094699A1|2016-11-23|
    FR3016368B1|2017-06-23|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2904524A|1957-01-02|1959-09-15|Armstrong Cork Co|Cork composition containing epoxy resin|
    US2993014A|1957-10-21|1961-07-18|Wilson Products Mfg Company|Epoxy resin composition containing cork or balsa wood and preparation of expanded product therefrom|
    US3457202A|1966-03-09|1969-07-22|Armstrong Cork Co|Cork-rubber gasketing and cushioning composition containing low density cellular rubber particles and a thermosetting binder|
    US8283394B2|2006-02-13|2012-10-09|Wacker Chemie Ag|Process for producing mouldings from cork particles|
    EP3238750A1|2016-04-29|2017-11-01|C.O.P.|Orthotic device made of natural fibres and a polyepoxide resin without bisphenol a, in particular biosourced|
    FR3058419A1|2016-11-04|2018-05-11|Diam Bouchage|COMPOSITION COMPRISING LIEGE PELLETS AND A HYDROPHOBIC SUBSTANCE EMULSION, AND PLUG PREPARED THEREFROM|
    CN110476122A|2017-03-31|2019-11-19|学校法人关西大学|Compound, the anti-corrosion agent composition comprising compound and the pattern forming method using it|
    CN111015884A|2018-10-10|2020-04-17|中国科学院理化技术研究所|Light wood-based material and preparation method thereof|
    法律状态:
    2015-10-14| PLFP| Fee payment|Year of fee payment: 3 |
    2016-10-19| PLFP| Fee payment|Year of fee payment: 4 |
    2018-01-10| PLFP| Fee payment|Year of fee payment: 5 |
    2018-10-18| PLFP| Fee payment|Year of fee payment: 6 |
    2019-08-16| TQ| Partial transmission of property|Owner name: DIAM BOUCHAGE, FR Effective date: 20190711 Owner name: CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE (, FR Effective date: 20190711 Owner name: UNIVERSITE DE MONTPELLIER, FR Effective date: 20190711 Owner name: ECOLE NATIONALE SUPERIEURE DE CHIMIE DE MONTPE, FR Effective date: 20190711 |
    2019-11-20| PLFP| Fee payment|Year of fee payment: 7 |
    2021-03-24| PLFP| Fee payment|Year of fee payment: 8 |
    2021-10-27| PLFP| Fee payment|Year of fee payment: 9 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1450319A|FR3016368B1|2014-01-15|2014-01-15|POLYEPOXIDE BOND / BINDER ASSOCIATION AND PROCESS FOR PREPARING THE SAME|FR1450319A| FR3016368B1|2014-01-15|2014-01-15|POLYEPOXIDE BOND / BINDER ASSOCIATION AND PROCESS FOR PREPARING THE SAME|
    PCT/EP2015/050684| WO2015107114A1|2014-01-15|2015-01-15|Combination of cork / polyepoxide binder and method for manufacturing same|
    ES15700674T| ES2719554T3|2014-01-15|2015-01-15|Cork / binder combination based on polyand preparation procedure|
    EP15700674.3A| EP3094699B1|2014-01-15|2015-01-15|Combination of cork / polyepoxide binder and method for manufacturing same|
    PT15700674T| PT3094699T|2014-01-15|2015-01-15|Combination of cork / polyepoxide binder and method for manufacturing same|
    [返回顶部]