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
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
  • C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic acids
• • A—HUMAN NECESSITIES
  • A43—FOOTWEAR
  • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
  • A43B1/00—Footwear characterised by the material
  • A43B1/14—Footwear characterised by the material made of plastics
• • A—HUMAN NECESSITIES
  • A43—FOOTWEAR
  • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
  • A43B13/00—Soles; Sole-and-heel integral units
  • A43B13/02—Soles; Sole-and-heel integral units characterised by the material
  • A43B13/04—Plastics, rubber or vulcanised fibre
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
• • 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
  • C08G2410/00—Soles
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
  • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
  • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
  • Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article

Definitions

• COPOLYAMIDE COMPOSITION COMPRISING SUCH COPOLYAMIDE
• the present invention relates to a copolyamide, its method of preparation and its uses, particularly in the manufacture of various objects combining transparency, ease of decoration and mechanical resistance to repeated solicitations.
• objects include consumer goods such as sports goods and, more specifically, sports shoes.
• the invention also relates to a composition comprising such a copolyamide as well as to the uses of this composition, in particular in the manufacture of all or part of the objects mentioned above.
• the present invention finally relates to a shoe, and in particular to a sports shoe implementing this copolyamide or this composition.
• sole means in the present description, the sole in its general sense, but also elements of the shoe and the damping system, and in particular the midsole or outsole.
• thermoplastic polymers are currently available on the market for the production of sports shoe soles.
• polyamides are commonly used, in particular amorphous polyamides.
• Such polyamides are particularly interesting because they have very good mechanical properties and are also transparent. However, they do not respond to the fatigue test "Ross Flex” and therefore can not be used for the realization of parts stressed in repeated bending.
• US 2008/01 19632 discloses a transparent composition comprising a copolyamide for the manufacture of printable transparent articles. These articles are more particularly in the form of films intended to constitute ski tops.
• the copolyamide of the composition comprises:
• Such a copolyamide meets the three criteria of rigidity, transparency and fatigue stated above.
• the transformation or shaping of such a copolyamide by molding is not at all satisfactory. Not only is the formation of bubbles in the molded mass observed, but the demolding operation is difficult, the copolyamide sticking to the walls of the mold. Therefore, the use of such a copolyamide for producing, by molding, shoe soles is not conceivable.
• the object of the present invention is therefore to provide a polymer which simultaneously satisfies the three criteria of rigidity, transparency and fatigue above and which can be easily implemented by molding, in particular for the production of molded articles such as than a shoe sole.
• A is an aliphatic repeating unit chosen from a unit obtained from at least one amino acid and a unit obtained from at least one lactam
• XY denotes a repeating unit obtained from the polycondensation of at least one diamine cycloaliphatic and at least one dicarboxylic acid comprising from 4 to 36 carbon atoms, advantageously from 6 to 18 carbon atoms,
• the weight proportion in pattern A in the copolyamide A X.Y is greater than or equal to 91%.
• the present invention also relates to a process for the preparation of a copolyamide, to its uses as well as to a composition comprising such a copolyamide and to the uses of such a composition.
• the present invention also relates to a shoe, and in particular to a sports shoe.
• copolyamide according to the invention comprises at least two distinct repeating units corresponding to the following general formulation:
• A is an aliphatic repeating unit chosen from a unit obtained from at least one amino acid and a unit obtained from at least one lactam
• XY denotes a repeating unit obtained from the polycondensation of at least one diamine cycloaliphatic and at least one dicarboxylic acid comprising from 4 to 36 carbon atoms, preferably from 6 to 18 carbon atoms.
• the proportion by weight of repeating unit A is greater than or equal to 91%. Therefore, the repeat pattern content X.Y is less than or equal to 9%.
• This proportion by weight in unit A is advantageously between 91.5% and 99%, advantageously from 91.5% to 97%, more preferably between 92% and 95%, particularly from 92% to 94%, and advantageously from 92% to 93%, 3%, the 100% complement corresponding to the weight proportion of the repeating pattern XY
• the repeating unit A is obtained from an aminocarboxylic acid comprising from 9 to 12 carbon atoms. It may thus be chosen from 9-aminononanoic acid (denoted 9), 10-aminodecanoic acid (denoted 10), 11-aminoundecanoic acid (denoted 1 1) and 12-aminododecanoic acid (denoted 12). ).
• the repeating unit A is obtained from 11-aminoundecanoic acid (1 1).
• the repeating unit A is obtained from a lactam comprising from 9 to 12 carbon atoms. It may thus be chosen from decanolactam (denoted 10), undecanolactam (denoted 1 1) and laurolactam or lauryllactam (denoted 12).
• the repeating unit A is obtained from lauryllactam (12).
• the repeating unit A is obtained from a single aminocarboxylic acid or a single lactam.
• the repeating unit A is obtained from a single aminocarboxylic acid or a single lactam.
• the repeat unit X.Y is a unit obtained from the polycondensation of at least one cycloaliphatic diamine and at least one dicarboxylic acid.
• the molar proportions of cycloaliphatic diamine and dicarboxylic acid are preferably stoichiometric.
• the cycloaliphatic diamine and the dicarboxylic acid each comprise from 4 to 36 carbon atoms and advantageously from 6 to 18 carbon atoms.
• the cycloaliphatic diamine may be chosen from bis (3,5-dialkyl-4-aminocyclohexyl) -methane, bis (3,5-dialkyl-4-aminocyclohexyl) ethane and bis (3,5-dialkyl-4-aminocyclohexyl) ) -propane, bis (3,5-dialkyl-4-aminocyclohexyl) butane, bis (3-methyl-4-aminocyclohexyl) -methane or 3'-dimethyl-4,4'-diamino-dicyclohexyl methane commonly referred to as "BMACM” or "MACM” (and noted B hereinafter), p-bis (aminocyclohexyl) -methane commonly known as "PACM” (and noted hereinafter P), isopropylidene di (cyclohexylamine) commonly referred to as "PACP”, isophorone di
• the cycloaliphatic diamine of the XY unit is chosen from 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane (B), p-bis (aminocyclohexyl) methane (P) and isophoronediamine (IPD). .
• the cycloaliphatic diamine of the XY unit is a bicycloaliphatic diamine, in particular chosen from 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane (B), p-bis (aminocyclohexyl) methane (P).
• the dicarboxylic acid may be chosen from linear or branched aliphatic dicarboxylic acids, cycloaliphatic dicarboxylic acids and aromatic dicarboxylic acids.
• the dicarboxylic acid may be chosen from linear aliphatic dicarboxylic acids, cycloaliphatic dicarboxylic acids and aromatic dicarboxylic acids.
• the dicarboxylic acid is aliphatic and linear, it can be chosen from succinic acid (4), pentanedioic acid (5), adipic acid (6), heptanedioic acid (7), acid octanedioic acid (8), azelaic acid (9), sebacic acid (10), undecanedioic acid (1 1), dodecanedioic acid (12), brassylic acid (13), tetradecanedioic acid (14), hexadecanedioic acid (16), octadecanedioic acid (18), octadecenedioic acid (18), eicosanedioic acid (20), docosanedioic acid (22) and fatty acid dimers containing 36 carbons.
• succinic acid (4) pentanedioic acid (5), adipic acid (6), heptanedioic acid (7), acid
• the fatty acid dimers mentioned above are dimerized fatty acids obtained by oligomerization or polymerization of unsaturated monobasic fatty acids with a long hydrocarbon chain (such as linoleic acid and oleic acid), as described in particular in the document EP 0 471 566.
• the dicarboxylic acid of the XY unit is an aliphatic dicarboxylic acid chosen from adipic acid (6), decanedioic acid (10), dodecanedioic acid (12) and tetradecanedioic acid (14). .
• copolyamides A XY when an aliphatic dicarboxylic acid is used, particular mention will be made of copolyamides corresponding to one of the formulas chosen from 1 1 / B.6, 1 1 / P.6 , 1 1 / IPD.6, 12 / B.6, 12 / P.6, 12 / IPD.6, 1 1 / B.10, 1 1 / P.10, 1 1 / IPD.10, 12 / B .10, 12 / P.10,
• the dicarboxylic acid when it is cycloaliphatic, it may comprise the following carbon skeletons: norbornyl methane, cyclohexane, cyclohexylmethane, dicyclohexylmethane, dicyclohexylpropane, di (methylcyclohexyl) or di (methylcyclohexyl) propane.
• the dicarboxylic acid When the dicarboxylic acid is aromatic, it may be chosen from terephthalic acid (denoted T), isophthalic acid (denoted I) and a naphthalenic acid.
• the dicarboxylic acid of the X.Y unit is an aromatic dicarboxylic acid, preferably isophthalic acid (I).
• the X.Y repeating unit is obtained from at least one cycloaliphatic diamine, in particular a bicycloaliphatic diamine and a single dicarboxylic acid, this dicarboxylic acid being preferably an aromatic dicarboxylic acid.
• the repeating unit X.Y is obtained from a single cycloaliphatic diamine, in particular a bicycloaliphatic diamine, and a single dicarboxylic acid, this dicarboxylic acid being preferably an aromatic dicarboxylic acid.
• the copolyamide according to the invention consists of only two repeating units A and X.Y:
• repeating unit A being a unit obtained either from a single aminocarboxylic acid or from a single lactam
• the repeating unit being obtained from the polycondensation of a single cycloaliphatic diamine, in particular a single bicycloaliphatic diamine and a single dicarboxylic acid, this dicarboxylic acid being preferably an aromatic dicarboxylic acid.
• the invention also relates to a process for preparing a copolyamide as defined above.
• This process comprises at least one step of polycondensation of the comonomers leading to the repeating units A and XY, that is to say that it comprises at least one polycondensation step of at least one aminocarboxylic acid and / or at least one lactam with at least one cycloaliphatic diamine, in particular a bicycloaliphatic diamine and at least one dicarboxylic acid, especially a dicarboxylic acid chosen from linear aliphatic dicarboxylic acids, cycloaliphatic dicarboxylic acids and aromatic dicarboxylic acids.
• the invention also relates to a composition comprising at least one copolyamide as described above.
• a composition according to the invention may comprise, in addition to the copolyamide that has just been described, at least one second polymer.
• this second polymer may be chosen from a semi-crystalline polyamide, an amorphous polyamide, a semi-crystalline copolyamide, an amorphous copolyamide, a polyetheramide, a polyetheramide, a polyesteramide and their mixtures.
• composition according to the invention may also comprise at least one additive.
• This additive may especially be chosen from fillers, fibers, dyes, stabilizers (in particular UV stabilizers), plasticizers, impact modifiers, surfactants, pigments, brighteners, antioxidants and waxes. and their mixtures.
• fillers there may be mentioned talc, silica, carbon black, carbon nanotubes, expanded graphite, titanium oxide or glass beads.
• copolyamide according to the invention or the composition according to the invention can be used to form a structure.
• This structure may be monolayer when it is formed only copolyamide or the composition according to the invention.
• This structure may also be a multilayer structure, when it comprises at least two layers and that at least one of the various layers forming the structure is formed from the copolyamide or the composition according to the invention.
• the structure may especially be in the form of fibers, a film, a sheet, a tube, a hollow body, a molded part or an injected part.
• Such structures particularly when in the form of film or sheet, may be decorated. These structures can be used to make objects, especially with the implementation of an over-injection step for obtaining parts.
• copolyamide according to the invention or the composition according to the invention can advantageously be used for the manufacture of a transparent molded article.
• Such an article may be a sole of a shoe or a constituent element of a shoe sole, in particular a sole of a sports shoe or a sole element of a sports shoe.
• copolyamide according to the invention or the composition according to the invention can also be used for the manufacture of ski tops; in particular, the copolyamide or the composition may be converted into films or sheets, the latter possibly being decorated, and then implemented by overmolding processes.
• copolyamide according to the invention or the composition according to the invention can also be used for the manufacture of photovoltaic panels.
• the present invention finally relates to a shoe, and in particular a sports shoe, this shoe comprising a sole.
• this sole is made in whole or in part from the copolyamide or the composition according to the invention.
• sole the sole in its general sense, but also elements of the shoe and the damping system, including the midsole or outsole.
• copolyamides 11, 12, C1, C2 and C3 are as follows:
• the copolyamide 11 was prepared from the weight contents of the following various compounds:
• hypophosphorous acid H 3 PO 2
• the above comonomers are introduced into a 92 I autoclave reactor which, once closed, is inerted under nitrogen and heated with stirring (40 rpm) at 240 ° C. under a pressure of 30 bar. The pressure is then decreased to atmospheric pressure to obtain a temperature of 270 ° C. The reactor is then degassed by a nitrogen sweep to reach the pair giving an inherent viscosity of between 1.10 to 1.60 dl / g (the inherent viscosity being measured from 0.5 g of copolyamide solubilized at 25.degree. metacresol).
• the copolyamide obtained is then extruded in the form of rods, cooled in a water tray at room temperature, and then granulated.
• the granules obtained are then dried at 80 ° C. for 12 hours under vacuum to reach a moisture content of less than 0.1%.
• Flexural modulus Traction test specimens were made from copolyamides 11, 12 and C1 to C3 to determine flexural modulus values in accordance with ISO 527. The desired flexural modulus should be between 1000 and 1500 MPa.
• Ross Flex fatigue test: this test is performed according to ASTM D1052. 2 mm thick pieces were made from the copolyamides 11, I2 and C1 to C3. These parts were pierced with a 2.5 mm diameter hole and then conditioned for 15 days at 23 ° C at 50% relative humidity. By this test called “Ross Flex", one determines the number of times at the end of which the piece, bent at the height of the hole at 60 ° and at a temperature of -10 °, breaks. It is considered that the part fulfills the conditions of this test when the number of cycles is greater than or equal to 50000.
• copolyamides 11 and 12 meet the criteria of transparency, rigidity and the so-called "Ross Flex" test.
• the molding transformation is quite satisfactory.
• copolyamides C2 and C3 it is observed that the product is long to crystallize, which implies a high cycle time. In addition, traces of flow are observed on the molded parts.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Proteomics, Peptides & Aminoacids (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Polyamides (AREA)
• Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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• 2012
  • 2012-09-04 FR FR1258232A patent/FR2994975B1/fr active Active
• 2013
  • 2013-08-27 CN CN201910881022.6A patent/CN110591085A/zh active Pending
  • 2013-08-27 US US14/425,957 patent/US20150225505A1/en not_active Abandoned
  • 2013-08-27 KR KR1020157004981A patent/KR102120506B1/ko active Active
  • 2013-08-27 EP EP13762190.0A patent/EP2892942B1/fr active Active
  • 2013-08-27 CN CN201910880639.6A patent/CN110606948A/zh active Pending
  • 2013-08-27 WO PCT/FR2013/051972 patent/WO2014037647A1/fr not_active Ceased
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