• 专利附录
  • 专利说明
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    • 专利摘要:
    The invention relates to a non-crosslinked polyamide block and polyether block copolymer foam, in which: the polyamide blocks of the copolymer have a number-average molecular weight of 200 to 1500 g / mol; the polyether blocks of the copolymer have a number-average molecular weight of 800 to 2500 g / mol; and the mass ratio of the polyamide blocks with respect to the polyether blocks of the copolymer is from 0.1 to 0.9. The invention also relates to a process for producing this foam and to articles manufactured therefrom.
    公开号:FR3047245A1
    申请号:FR1650719
    申请日:2016-01-29
    公开日:2017-08-04
    发明作者:Clio Cocquet；Quentin Pineau；Karine Loyen；Francois Fernagut；Helena Cheminet
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    COPOLYMER FOAM WITH POLYAMIDE BLOCKS AND BLOCKS
    POLYETHERS
    FIELD OF THE INVENTION
    The present invention relates to a foam formed from a polyamide block and polyether block copolymer and a process for producing the same.
    TECHNICAL BACKGROUND
    Various polymeric foams are used in particular in the field of sports equipment, such as insoles or soles components, gloves, rackets or golf balls, individual protection elements in particular for the practice of sport (vests, inner helmet parts) , hulls ...).
    Such applications require a set of particular physical properties that provide reboundability, low compression set, and the ability to withstand repeated impacts without deforming and returning to the original shape.
    EP 0405227 and EP 0402883 disclose foams made from various polymers and their use in shoe soles.
    EP 1650255 describes crosslinked foams obtained from polyamide block copolymers and polyether blocks.
    Cross-linked foams have the drawback of presenting significant constraints from a point of view of the manufacturing process: the manufacturing time is generally high, the manufacture is generally necessarily in batch mode only, and undesirable chemicals must be handled.
    In addition, crosslinked foams are difficult to recycle after use.
    WO 2013/148841 discloses a bilayer extrusion process from various polymers, including polyamide block copolymers and polyether blocks.
    WO 2015/052265 discloses a method for manufacturing expanded thermoplastic particles from any thermoplastic elastomeric polymer.
    In addition, Zotefoams sells cross-linked foams made from polyamide block copolymers and polyether blocks under the name ZOTEK®PEBA. The disadvantages of the crosslinking have been recalled above. In addition, the durability of the products is imperfect.
    There are also many foams made from thermoplastic polyurethane (TPU) or ethylene-vinyl acetate (EVA). These foams have a relatively low temperature range of use, as well as relatively low compression time deformation in short time, and imperfect durability. Their manufacturing processes are also binding.
    There is therefore a need to provide low density polymer foams, having one or more advantageous properties among: a high capacity to restore elastic energy during stress under low stress; low compression set; and high compressive fatigue resistance.
    SUMMARY OF THE INVENTION The invention relates firstly to a non-crosslinked polyamide block and polyether block copolymer foam, wherein: the polyamide blocks of the copolymer have a number average molecular weight of from 200 to 1500 g / mol; the polyether blocks of the copolymer have a number-average molecular weight of 800 to 2500 g / mol; and the mass ratio of the polyamide blocks with respect to the polyether blocks of the copolymer is from 0.1 to 0.9.
    According to one embodiment: the polyamide blocks of the copolymer have a number-average molar mass of from 400 to 1000 g / mol, preferably from 600 to 850 g / mol; the polyether blocks of the copolymer have a number-average molecular weight of 1000 to 2000 g / mol; and the mass ratio of the polyamide blocks with respect to the polyether blocks of the copolymer is from 0.3 to 0.6.
    According to one embodiment, the polyamide blocks of the copolymer are blocks of polyamide 11, or of polyamide 12, or of polyamide 6, or of polyamide 6.10.
    According to one embodiment, the polyether blocks of the copolymer are blocks of polyethylene glycol or of polytetrahydrofuran.
    According to one embodiment, the foam has a density of less than or equal to 800 kg / m3, preferably less than or equal to 600 kg / m3, more particularly preferably less than or equal to 400 kg / m3, or even less than or equal to 300 kg / m3.
    According to one embodiment, the foam also contains one or more additives, preferably chosen from copolymers of ethylene and vinyl acetate, copolymers of ethylene and of acrylate, and copolymers of ethylene and alkyl ( meth) acrylate. The invention also relates to a process for manufacturing this foam, comprising a step of mixing the copolymer in the molten state, optionally with one or more additives, and with an expansion agent, and a step of foaming the copolymer mixture. and expansion agent.
    In one embodiment, the blowing agent is a physical blowing agent, preferably selected from dinitrogen, carbon dioxide, hydrocarbons, chlorofluorocarbons, hydrochlorocarbons, hydrofluorocarbons and hydrochlorofluorocarbons.
    According to one embodiment, the method comprises a step of injecting the mixture of copolymer and blowing agent into a mold, the foaming of the mixture being carried out by the opening of the mold. The invention also relates to an article consisting of the foam above. The invention also relates to an article comprising at least one element consisting of the foam above.
    According to one embodiment, the article of the invention is chosen from soles of sports shoes, balloons or balls, gloves, personal protective equipment, soles for rails, automobile parts, construction parts. and parts of electrical and electronic equipment.
    The present invention overcomes the disadvantages of the state of the art. It more particularly provides low density polymer foams, having one or more advantageous properties among: a high capacity to restore elastic energy during stress under low stress; low compression set; and high compressive fatigue resistance.
    Advantageously, these properties are obtained over a wide temperature range, preferably from -20 ° C to 50 ° C, or even from -30 ° C to 80 ° C.
    This is accomplished through the use of a non-crosslinked polyamide block and polyether block copolymer, characterized by particular ranges of molecular weight for the polyamide blocks and polyether blocks, as well as a particular range of mass ratio between the polyether blocks and the polyether blocks. polyamide blocks and polyether blocks.
    BRIEF DESCRIPTION OF THE FIGURES
    FIG. 1 represents the results of measurements of remanent deformation after a fatigue test carried out on a foam according to the invention and on a control foam (see example 2). The relaxation time (in hours) is shown on the abscissa, and the percentage of residual deformation is indicated on the ordinate.
    DESCRIPTION OF EMBODIMENTS OF THE INVENTION The invention is now described in more detail and in a nonlimiting manner in the description which follows. The invention uses a copolymer with polyamide blocks and polyether blocks, or "PEBA".
    PEBAs result from the polycondensation of polyamide blocks with reactive ends with polyether blocks with reactive ends, such as, inter alia, the polycondensation of: 1) polyamide blocks with diamine chain ends with polyoxyalkylene blocks with dicarboxylic chain ends; 2) polyamide blocks with dicarboxylic chain ends with polyoxyalkylene blocks with diamine chain ends, obtained for example by cyanoethylation and hydrogenation of aliphatic α, ω-dihydroxylated polyoxyalkylene blocks called polyetherdiols; 3) polyamide blocks with dicarboxylic chain ends with polyetherdiols, the products obtained being, in this particular case, polyetheresteram ides.
    The polyamide blocks with dicarboxylic chain ends come, for example, from the condensation of polyamide precursors in the presence of a chain-limiting dicarboxylic acid. The polyamide blocks with diamine chain ends come for example from the condensation of polyamide precursors in the presence of a chain-limiting diamine.
    Three types of polyamide blocks can advantageously be used.
    According to a first type, the polyamide blocks come from the condensation of a dicarboxylic acid, in particular those having from 4 to 20 carbon atoms, preferably those having from 6 to 18 carbon atoms, and an aliphatic or aromatic diamine , in particular those having 2 to 20 carbon atoms, preferably those having 6 to 14 carbon atoms. Examples of dicarboxylic acids that may be mentioned include 1,4-cyclohexyldicarboxylic acid, butanedioic, adipic, azelaic, suberic, sebacic, dodecanedicarboxylic, octadecanedicarboxylic acids and terephthalic and isophthalic acids, but also dimerized fatty acids. . Examples of diamines that may be mentioned include tetramethylenediamine, hexamethylenediamine, 1,10-decamethylenediamine, dodecamethylenediamine, trimethylhexamethylenediamine, the isomers of bis (4-aminocyclohexyl) methane (BACM), bis - (3-methyl-4-aminocyclohexyl) methane (BMACM), and 2-2-bis (3-methyl-4-aminocyclohexyl) propane (BMACP), para-amino-di-cyclohexyl methane ( PACM), isophoronediamine (IPDA), 2,6-bis- (aminomethyl) -norbornane (BAMN) and piperazine (Pip).
    Advantageously, polyamide blocks PA 4.12, PA 4.14, PA 4.18, PA 6.10, PA 6.12, PA 6.14, PA 6.18, PA 9.12, PA 10.10, PA 10.12, PA 10.14 and PA 10.18 are used. In the notation PA X.Y, X represents the number of carbon atoms derived from the diamine residues, and Y represents the number of carbon atoms derived from the diacid residues, in a conventional manner.
    According to a second type, the polyamide blocks result from the condensation of one or more α, ω-aminocarboxylic acids and / or one or more lactams having from 6 to 12 carbon atoms in the presence of a dicarboxylic acid having from 4 to at 12 carbon atoms or diamine. Examples of lactams include caprolactam, oenantholactam and lauryllactam. As examples of α, ω-amino carboxylic acid, mention may be made of aminocaproic acid, amino-7-heptanoic acid, amino-11-undecanoic acid and amino-12-dodecanoic acid.
    Advantageously, the polyamide blocks of the second type are blocks of PA 11 (polyundecanamide), PA 12 (polydodecanamide) or PA 6 (polycaprolactam). In the notation PA X, X represents the number of carbon atoms derived from the amino acid residues.
    According to a third type, the polyamide blocks result from the condensation of at least one α, ω-aminocarboxylic acid (or a lactam), at least one diamine and at least one dicarboxylic acid.
    In this case, the polyamide PA blocks are prepared by polycondensation of: - the linear or aromatic aliphatic diamine or diamines having X carbon atoms; - Dicarboxylic acid (s) having Y carbon atoms; and - comonomers {Z}, chosen from lactams and α, ω-aminocarboxylic acids having Z carbon atoms and equimolar mixtures of at least one diamine having X 1 carbon atoms and at least one dicarboxylic acid having Y1 carbon atoms, (X1, Y1) being different from (X, Y), - said at least one comonomer (Z) being introduced in a proportion by weight of preferably up to 50%, preferably up to 20%, even more advantageously up to 10% with respect to all of the polyamide precursor monomers; in the presence of a chain limiter chosen from dicarboxylic acids.
    Advantageously, the dicarboxylic acid having Y carbon atoms, which is introduced in excess with respect to the stoichiometry of the diamine or diamines, is used as chain limiter.
    According to a variant of this third type, the polyamide blocks result from the condensation of at least two α, ω-aminocarboxylic acids or of at least two lactams having from 6 to 12 carbon atoms or of a lactam and a aminocarboxylic acid having not the same number of carbon atoms in the possible presence of a chain limiter. As examples of aliphatic α, ω-aminocarboxylic acid, mention may be made of aminocaproic, amino-7-heptanoic, amino-11-undecanoic and amino-12-dodecanoic acids. Examples of lactam include caprolactam, oenantholactam and lauryllactam. As examples of aliphatic diamines, mention may be made of hexamethylenediamine, dodecamethylenediamine and trimethylhexamethylenediamine. As examples of cycloaliphatic diacids, mention may be made of 1,4-cyclohexyldicarboxylic acid. As examples of aliphatic diacids, mention may be made of butanedioic acid, adipic acid, azelaic acid, suberic acid, sebacic acid, dodecanedicarboxylic acid and dimerized fatty acid. These dimerized fatty acids preferably have a dimer content of at least 98%; preferably they are hydrogenated; these are, for example, products sold under the trademark "PRIPOL" by the company "Croda", or under the trademark EMPOL by the company BASF, or under the trademark Radiacid by the company OLEON, and polyoxyalkylenes α, ω-diacids . As examples of aromatic diacids, mention may be made of terephthalic (T) and isophthalic (I) acids. By way of examples of cycloaliphatic diamines, mention may be made of the isomers of bis (4-aminocyclohexyl) methane (BACM), bis (3-methyl-4-aminocyclohexyl) methane (BMACM) and 2-2-bis- (3-methyl-4-aminocyclohexyl) propane (BMACP), and para-amino-di-cyclohexyl methane (PACM). Other diamines commonly used may be isophoronediamine (IPDA), 2,6-bis (aminomethyl) -norbornane (BAMN) and piperazine. By way of examples of polyamide blocks of the third type, mention may be made of the following: PA 6.6 / 6, in which 6.6 denotes hexamethylenediamine units condensed with adipic acid and 6 denotes units resulting from the condensation of caprolactam; PA 6.6 / 6.10 / 11/12, where 6.6 denotes hexamethylenediamine condensed with adipic acid, 6.10 denotes hexamethylenediamine condensed with sebacic acid, 11 denotes units resulting from the condensation of aminoundecanoic acid and 12 denotes patterns resulting from the condensation of lauryllactam.
    PAX / Y, PAX / Y / Z notations, etc. relate to copolyamides in which X, Y, Z, etc. represent homopolyamide units as described above.
    Advantageously, the polyamide blocks of the copolymer used in the invention comprise polyamide blocks PA 6, PA 11, PA 12, PA 5.4, PA 5.9, PA 5.10, PA 5.12, PA 5.13, PA 5.14, PA 5.16, PA 5.18, PA 5.36, PA 6.4, PA 6.9, PA 6.10, PA 6.12, PA 6.13, PA 6.14, PA 6.16, PA 6.18, PA 6.36, PA 10.4, PA 10.9, PA 10.10, PA 10.12, PA 10.13, PA 10.14, PA 10.16. , PA 10.18, PA 10.36, PA 10.T, PA 12.4, PA 12.9, PA 12.10, PA 12.12, PA 12.13, PA 12.14, PA 12.16, PA 12.18, PA 12.36, PA 12.T, or mixtures or copolymers of these; and preferably comprise polyamide blocks PA 6, PA 11, PA 12, PA 6.10, PA 10.10, PA 10.12, or mixtures or copolymers thereof.
    The polyether blocks consist of alkylene oxide units.
    The polyether blocks can in particular be PEG (polyethylene glycol) blocks, ie consisting of ethylene oxide units, and / or PPG (propylene glycol) blocks, ie consisting of propylene oxide units, and / or or P03G (polytrimethylene glycol) blocks, that is to say consisting of glycol polytrimethylene ether units, and / or PTMG blocks, ie consisting of tetramethylene glycol units also called polytetrahydrofuran units. The PEBA copolymers may comprise in their chain several types of polyethers, the copolyethers may be block or statistical.
    It is also possible to use blocks obtained by oxyethylation of bisphenols, such as, for example, bisphenol A. These latter products are described in particular in document EP 613919.
    The polyether blocks may also consist of ethoxylated primary amines. By way of example of ethoxylated primary amines, mention may be made of the products of formula:
    in which m and n are integers between 1 and 20 and x an integer between 8 and 18. These products are for example commercially available under the trade name NORAMOX® from CECA and under the brand GENAMIN® from the company Clariant.
    The flexible polyether blocks may comprise polyoxyalkylene blocks with NH 2 chain ends, such blocks being obtainable by cyanoacetylation of aliphatic α, ω-dihydroxylated polyoxyalkylene blocks known as polyetherdiols. More particularly, Jeffamine or Elastamine commercial products may be used (e.g., Jeffamine® D400, D2000, ED 2003, XTJ 542, Huntsman commercial products, also described in JP 2004346274, JP 2004352794 and EP 1482011).
    The polyetherdiol blocks are either used as such and copolycondensed with polyamide blocks having carboxylic ends, or aminated to be converted into polyether diamines and condensed with polyamide blocks having carboxylic ends. The general two-step preparation method for PEBA copolymers having ester bonds between PA blocks and PE blocks is known and is described, for example, in FR 2846332. The general method for preparing the PEBA copolymers of the invention having amide linkages between the PA blocks and the PE blocks is known and described, for example in EP 1482011. The polyether blocks can also be mixed with polyamide precursors and a diacid chain limiter to prepare the polyamide block polymers. and polyether blocks having statistically distributed patterns (one-step process).
    Of course, the PEBA designation in the present description of the invention relates as well to PEBAX® marketed by Arkema, Vestamid® marketed by Evonik®, Grilamid® marketed by EMS, Pelestat PEBA type marketed by Sanyo or any other PEBA from other suppliers.
    If the block copolymers described above generally comprise at least one polyamide block and at least one polyether block, the present invention also covers all copolymer alloys comprising two, three, four or more different blocks selected from those described in US Pat. the present description, since these blocks comprise at least polyamide blocks and polyethers.
    For example, the copolymer alloy according to the invention may comprise a block segmented copolymer comprising three different types of blocks (or "triblock"), which results from the condensation of several of the blocks described above. Said triblock is preferably chosen from copolyetheresteramides and copolyetheramideurethanes.
    Particularly preferred PEBA copolymers in the context of the invention are copolymers comprising blocks: PA 11 and PEG; - PA 11 and PTMG; PA 12 and PEG; PA 12 and PTMG; - PA 6.10 and PEG; - PA 6.10 and PTMG; PA 6 and PEG; - PA 6 and PTMG.
    The foam of the invention comprises a PEBA copolymer as described above: preferably only one such copolymer is used. However, it is possible to use a mixture of two or more PEBA copolymers as described above.
    According to the invention, the number-average molar mass of the polyamide blocks in the PEBA copolymer is 200 to 1500 g / mol; the number-average molar mass of the polyether blocks is from 800 to 2500 g / mol; and the mass ratio of the polyamide blocks with respect to the polyether blocks of the copolymer is from 0.1 to 0.9.
    The number average molecular weight is set by the chain limiter content. It can be calculated according to the relation:
    In this formula, the monomer represents the number of moles of monomer, the acid number represents the number of moles of diacid limiter in excess, MWmotif of repetition represents the molar mass of the repeating unit, and MWdiacid represents the molar mass of the excess diacid.
    According to particular embodiments, the copolymers are defined by the following ranges of average molar masses Mn:
    In addition, according to the invention, the mass ratio of the polyamide blocks with respect to the polyether blocks of the copolymer is from 0.1 to 0.9. This mass ratio can be calculated by dividing the average number-average molecular weight of the polyamide blocks by the average shadow mass of the polyether blocks.
    According to particular embodiments, this ratio is from 0.1 to 0.2; or 0.2 to 0.3; or from 0.3 to 0.4; or from 0.4 to 0.5; or from 0.5 to 0.6; or from 0.6 to 0.7; or 0.7 to 0.8; or from 0.8 to 0.9.
    Preferably, the copolymer used in the invention has an instantaneous hardness of less than or equal to 40 Shore D, more preferably less than or equal to 35 Shore D. The hardness measurements can be carried out according to the ISO 868 standard.
    The polyamide block and polyether block copolymer is used to form a foam without a crosslinking step. The foam is formed by mixing the copolymer in the molten state with an expanding agent and then performing a foaming step.
    According to one embodiment, the foam thus formed consists essentially or even consists of the copolymer described above (or the copolymers, if a mixture of copolymers is used) and optionally the blowing agent, if this remains present in the pores of the foam, especially if it is a closed pore foam.
    The polyamide block and polyether block copolymer may be combined with various additives, for example copolymers of ethylene and vinyl acetate or EVA (for example those marketed under the name Evatane® by Arkema), or copolymers of ethylene and acrylate, or copolymers of ethylene and alkyl (meth) acrylate, for example those marketed under the name Lotryl® by Arkema. These additives can
    allow to adjust the hardness of the foamed piece, its appearance and its comfort. The additives may be added in a content of from 0 to 50% by weight, preferably from 5 to 30% by weight, relative to the polyamide block and polyether block copolymer. The blowing agent may be a chemical or physical agent. Preferably, it is a physical agent, such as for example dinitrogen or carbon dioxide, or a hydrocarbon, chlorofluorocarbon, hydrochlorocarbon, hydrofluorocarbon or hydrochlorofluorocarbon (saturated or unsaturated). For example, butane or pentane may be used.
    A physical blowing agent is mixed with the copolymer in liquid or supercritical form, and then converted into a gas phase during the foaming step.
    According to a preferred embodiment, the mixture of the copolymer and the blowing agent is injected into a mold, and the foaming is produced by the opening of the mold. This technique makes it possible to directly produce three-dimensional foamed objects with complex geometries.
    It is also a relatively simple technique to implement, particularly with respect to certain processes for melting foamed particles as described in the prior art: in fact, the filling of the mold with foamed pellets of polymer then the melting of the particles to ensure a mechanical strength of the parts without destroying the structure of the foam are complex operations. Other foaming techniques that can be used include "batch" foaming and extrusion foaming.
    The foam produced according to the invention preferably has a density of 50 to 800 kg / m3, and more preferably 100 to 600 kg / m3. Density control can be achieved by adapting the parameters of the manufacturing process.
    Preferably, this foam has a rebound resilience, according to ISO 8307, greater than or equal to 55%.
    Preferably, this foam has a compression set, according to the ISO 7214 standard, less than or equal to 10%, and more preferably less than or equal to 8%.
    Preferably, this foam also has excellent properties of fatigue resistance and damping.
    The foam according to the invention can be used to manufacture sports equipment, such as soles of sports shoes, ski boots, midsoles, insoles, or functional components of insoles, in the form of inserts in different parts of the sole (heel or arch for example), or the components of the tops of shoes in the form of reinforcements or inserts in the structure of the shoe upper, in the form of protections.
    It can also be used to make balloons, sports gloves (eg football gloves), components of golf balls, snowshoes, protective elements (vests, inner helmet elements, cockles ... ).
    The foam according to the invention has anti-shock, anti-vibration and anti-noise properties of interest, combined with haptic properties suitable for capital goods. It can therefore also be used for the manufacture of railway track soles, or various parts in the automotive industry, in transport, in electrical and electronic equipment, in construction or in the manufacturing industry.
    An advantage of the foam objects according to the invention is that they can be easily recycled, for example by melting them in an extruder equipped with a degassing outlet (optionally after having cut into pieces).
    EXAMPLES
    The following examples illustrate the invention without limiting it.
    Example 1
    Different PEBA copolymers were tested, the characteristics of which are summarized in the table below:
    Tf denotes the melting temperature of the copolymer, and Te denotes its crystallization temperature. The polyether blocks are PTMG blocks for all of these copolymers.
    The copolymers A to D are according to the invention, and the copolymers E and F correspond to comparative examples.
    Foams are made from copolymers A through F using an Arburg Allrounder 270C injection press, with a Trexel II-type physical expansion agent injection system. The operating parameters are as follows: - Sleeve temperature: 160 to 210 ° C. - Injection speed: 112 cm / s. - Hold time before opening the mold: 25 to 40 s. - Cooling time: 120 to 180 s. - Mold temperature: 60 to 80 ° C. - Mold opening length: up to 12 mm. - Opening speed of the mold. 50 mm / s. - Total cycle time: 145 to 220 s. The foaming agent used is dinitrogen introduced at a level of 0.6% by weight.
    The thermoplastic polyurethane foam of the Infinergy brand (BASF) and a cross-linked EVA foam are also used as controls.
    Different properties of the foams obtained are evaluated: - density: according to the ISO 845 standard; - rebound resilience: according to ISO 8307 (a steel ball of 16.8 g and a diameter of 16 mm is dropped from a height of 500 mm on a foam sample, the rebounding resilience then corresponds to the percentage of energy returned to the ball, or percentage of the initial height reached by the ball rebound); - compression set: a measure is made of compressing a sample at a rate of deformation and for a given time, then releasing the relaxed stress, and
    note residual deformation after a recovery time; the measurement is adapted from the ISO 7214 standard, with a deformation of 50%, a holding time of 22 h, a temperature of 23 ° C, and taking a measurement after 30 min and another measurement after 24 h of recovery.
    Example 2
    In this example, a compressive fatigue test is carried out on the foam made with PEBA No. B at 200 kg / m3 and on a control TPU foam.
    The fatigue test is performed at a frequency of 1.5 Hz on a sample of 50 mm diameter and about 15 mm thick. A stress is applied which varies according to a sinusoidal signal between 0 and 360 kPa or between 0 and 720 kPa, using a hydraulic dynamometer (MTS810). After 350,000 cycles, the evolution of the thickness of the sample, which returns to its initial shape over time, is measured. An ideal material would instantly return to its original shape. The foams currently used have a residual deformation of the order of 10% after several days of relaxation.
    This fatigue test reproduces the mechanical stresses to which a foam sample is confronted, in particular in applications such as the soles of sports shoes.
    The results are shown in Figure 1. The curve marked with white squares corresponds to the control foam tested at 720 kPa. The curve marked with the white circles corresponds to the foam according to the invention
    tested at 720 kPa. The curve marked with the black circles corresponds to the control foam tested at 360 kPa. The curve marked with the gray crosses corresponds to the foam according to the invention tested at 360 kPa.
    It is found that the foam according to the invention returns to its initial shape (minimum residual deformation level) more rapidly than the control foam.
    权利要求:
    Claims (12)
    [1" id="c-fr-0001]
    1. Non-crosslinked polyamide block and polyether block copolymer foam, in which: the polyamide blocks of the copolymer have a number-average molecular weight of 200 to 1500 g / mol; the polyether blocks of the copolymer have a number-average molecular weight of 800 to 2500 g / mol; and the mass ratio of the polyamide blocks with respect to the polyether blocks of the copolymer is from 0.1 to 0.9.
    [2" id="c-fr-0002]
    2. Foam according to claim 1, in which: the polyamide blocks of the copolymer have a number-average molar mass of from 400 to 1000 g / mol, preferably from 600 to 850 g / mol; the polyether blocks of the copolymer have a number-average molecular weight of 1000 to 2000 g / mol; and the mass ratio of the polyamide blocks with respect to the polyether blocks of the copolymer is from 0.3 to 0.6.
    [3" id="c-fr-0003]
    3. Foam according to claim 1 or 2, wherein the polyamide blocks of the copolymer are blocks of polyamide 11, or polyamide 12, or polyamide 6, or polyamide 6.10.
    [4" id="c-fr-0004]
    4. Foam according to one of claims 1 to 3, wherein the polyether blocks of the copolymer are blocks of polyethylene glycol or polytetrahydrofuran.
    [5" id="c-fr-0005]
    5. Foam according to one of claims 1 to 4, which has a density of less than or equal to 800 kg / m3, preferably less than or equal to 600 kg / m3, more preferably less than or equal to 400 kg / m3 or even less than or equal to 300 kg / m3.
    [6" id="c-fr-0006]
    Foam according to one of claims 1 to 5, which also contains one or more additives, preferably chosen from copolymers of ethylene and vinyl acetate, copolymers of ethylene and acrylate, and copolymers of ethylene and alkyl (meth) acrylate.
    [7" id="c-fr-0007]
    7. A method of manufacturing a foam according to one of claims 1 to 6, comprising a step of mixing the copolymer in the molten state, optionally with one or more additives, and with an expansion agent, and a step foaming the copolymer and blowing agent mixture.
    [8" id="c-fr-0008]
    The process according to claim 7, wherein the blowing agent is a physical blowing agent, preferably selected from dinitrogen, carbon dioxide, hydrocarbons, chlorofluorocarbons, hydrochlorocarbons, hydrofluorocarbons and hydrochlorofluorocarbons. .
    [9" id="c-fr-0009]
    9. Method according to one of claims 7 or 8, comprising a step of injecting the mixture of copolymer and blowing agent in a mold, the foaming of the mixture being effected by the opening of the mold.
    [10" id="c-fr-0010]
    10. Article consisting of a foam according to one of claims 1 to 6.
    [11" id="c-fr-0011]
    11. Article comprising at least one element made of a foam according to one of claims 1 to 6.
    [12" id="c-fr-0012]
    12. Article according to one of claims 10 or 11, which is selected from the soles of sports shoes, balls or balls, gloves, personal protective equipment, soles for rails, auto parts, parts of construction and parts of electrical and electronic equipment.
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    JP2019510840A|2019-04-18|
    US20190071570A1|2019-03-07|
    FR3047245B1|2018-02-23|
    EP3408317A1|2018-12-05|
    CN108884253A|2018-11-23|
    JP2022009161A|2022-01-14|
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    FR3047245B1|2016-01-29|2018-02-23|Arkema France|COPOLYMER FOAM WITH POLYAMIDE BLOCKS AND POLYETHERS BLOCKS|FR3047245B1|2016-01-29|2018-02-23|Arkema France|COPOLYMER FOAM WITH POLYAMIDE BLOCKS AND POLYETHERS BLOCKS|
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    法律状态:
    2016-12-15| PLFP| Fee payment|Year of fee payment: 2 |
    2017-08-04| PLSC| Publication of the preliminary search report|Effective date: 20170804 |
    2017-12-11| PLFP| Fee payment|Year of fee payment: 3 |
    2019-12-16| PLFP| Fee payment|Year of fee payment: 5 |
    2020-12-10| PLFP| Fee payment|Year of fee payment: 6 |
    2021-12-17| PLFP| Fee payment|Year of fee payment: 7 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1650719|2016-01-29|
    FR1650719A|FR3047245B1|2016-01-29|2016-01-29|COPOLYMER FOAM WITH POLYAMIDE BLOCKS AND POLYETHERS BLOCKS|FR1650719A| FR3047245B1|2016-01-29|2016-01-29|COPOLYMER FOAM WITH POLYAMIDE BLOCKS AND POLYETHERS BLOCKS|
    US16/071,351| US11008464B2|2016-01-29|2017-01-27|Copolymer foam with polyamide blocks and polyether blocks|
    EP17706847.5A| EP3408317A1|2016-01-29|2017-01-27|Copolymer foam with polyamide blocks and polyether blocks|
    PCT/FR2017/050187| WO2017129913A1|2016-01-29|2017-01-27|Copolymer foam with polyamide blocks and polyether blocks|
    JP2018539277A| JP6962922B2|2016-01-29|2017-01-27|Copolymer foam with polyamide block and polyether block|
    CN201780008391.3A| CN108884253A|2016-01-29|2017-01-27|Copolymer foam with polyamide-block and polyether block|
    US17/240,904| US20210324196A1|2016-01-29|2021-04-26|Copolymer Foam With Polyamide Blocks And Polyether Blocks|
    JP2021169180A| JP2022009161A|2016-01-29|2021-10-14|Copolymer foam with polyamide block and polyether block|
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