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  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/0066—Use of inorganic compounding ingredients
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  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
  • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
  • C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
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  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
  • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
  • C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
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  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/013—Fillers, pigments or reinforcing additives
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L87/00—Compositions of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
  • C08L87/005—Block or graft polymers not provided for in groups C08L1/00 - C08L85/04
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2201/00—Foams characterised by the foaming process
  • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
  • C08J2201/03—Extrusion of the foamable blend
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2203/00—Foams characterized by the expanding agent
  • C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2203/00—Foams characterized by the expanding agent
  • C08J2203/06—CO2, N2 or noble gases
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2203/00—Foams characterized by the expanding agent
  • C08J2203/10—Water or water-releasing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2203/00—Foams characterized by the expanding agent
  • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2203/00—Foams characterized by the expanding agent
  • C08J2203/16—Unsaturated hydrocarbons
• • C—CHEMISTRY; METALLURGY
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  • C08J2203/00—Foams characterized by the expanding agent
  • C08J2203/18—Binary blends of expanding agents
  • C08J2203/184—Binary blends of expanding agents of chemical foaming agent and physical blowing agent, e.g. azodicarbonamide and fluorocarbon
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  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2203/00—Foams characterized by the expanding agent
  • C08J2203/22—Expandable microspheres, e.g. Expancel®
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2205/00—Foams characterised by their properties
  • C08J2205/04—Foams characterised by their properties characterised by the foam pores
  • C08J2205/052—Closed cells, i.e. more than 50% of the pores are closed
• • C—CHEMISTRY; METALLURGY
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  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
  • C08J2371/02—Polyalkylene oxides
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  • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
  • C08J2375/04—Polyurethanes
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
  • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
  • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
  • C08J9/141—Hydrocarbons
• • C—CHEMISTRY; METALLURGY
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  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
  • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
  • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
  • C08J9/143—Halogen containing compounds
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  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
  • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
  • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
  • C08J9/143—Halogen containing compounds
  • C08J9/147—Halogen containing compounds containing carbon and halogen atoms only
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  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/24—Acids; Salts thereof
  • C08K3/26—Carbonates; Bicarbonates
  • C08K2003/262—Alkali metal carbonates

Definitions

• the present invention relates to a foam formed from a block copolymer and a method of making it.
• 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 especially for the practice of sport (vests, inner helmet parts) , shells ); in the field of insulation, including acoustic and / or thermal insulation.
• Such applications require a set of particular physical properties ensuring: lightness, reboundability, low permanent deformation in compression, ability to withstand repeated impacts without deforming and ability to return to the original form.
• 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.
• 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.
• the durability of the products is imperfect.
• TPU thermoplastic polyurethane
• EVA ethylene-vinyl acetate
• an uncrosslinked copolymer foam in particular a PEBA foam, characterized by:
• homogeneous cell sizes pores of the foam: the difference between their internal diameters (cell sizes in ⁇ ) does not exceed 30%, preferably not more than 20%, preferably not more than 10%,
• the size of the cells is measured by scanning electron microscopy (SEM) on a section of the foam.
• the D50 of the foam cells of the invention is in the range of 30 to 130 ⁇ .
• the D50 of the cells of a foam corresponds to the value of the cell size that divides the examined cell population exactly in half.
• 50% of the cells have a size of less than 130 ⁇ .
• the D50 can be measured according to ISO 9276 - Parts 1 to 6: "Representation of data obtained by particle size analysis".
• a MEB "Quanta 250" from the company FEI, and software (Fraunhofer) are used to obtain the cell size distribution of the foam and deduce the D50.
• the subject of the invention is therefore an uncrosslinked copolymer foam with rigid blocks and flexible blocks, characterized in that it is in the form of a polymer matrix containing closed pores or cells by closing off gas, said matrix comprising :
• said gas comprises at least one compound chosen from:
• said at least one block copolymer comprises at least one block chosen from: polyether blocks, polyester blocks, polyamide blocks, polyurethane blocks, and mixtures thereof.
• composition according to the invention Preferably, in the composition according to the invention:
• the rigid blocks of the copolymer have a number average molecular weight of 200 to 2000 g / mol;
• the soft blocks of the copolymer have a number average molecular weight of 800 to 2500 g / mol;
• the mass ratio of the polyamide blocks with respect to the polyether blocks of the copolymer is from 0.1 to 2.
• said copolymer comprises a copolymer with polyamide blocks and polyether blocks.
• the polyamide blocks of the copolymer are blocks of polyamide 11, polyamide 12, polyamide 6, polyamide 6.10, polyamide 6.12, polyamide 10.10, polyamide 10.12, and mixtures thereof.
• the polyether blocks of the copolymer are blocks of polyethylene glycol or polytetramethylene glycol.
• the foam composition according to the invention has a density of less than or equal to 800 kg / m 3 , preferably less than or equal to 700 kg / m 3 , preferably less than or equal to 600 kg / m 3 , preferably less than or equal to 500 kg / m 3 , preferably less than or equal to 400 kg / m 3 , more preferably less than or equal to 300 kg / m 3 , or even less than or equal to 200 kg / m 3 .
• the foam composition of the invention also contains from 0.1 to 50% by weight of one or more other polymers (different from the block copolymer according to the invention), preferably chosen from copolymers of ethylene and vinyl acetate, copolymers of ethylene and acrylate, and copolymers of ethylene and alkyl (meth) acrylate.
• one or more other polymers preferably chosen from copolymers of ethylene and vinyl acetate, copolymers of ethylene and acrylate, and copolymers of ethylene and alkyl (meth) acrylate.
• the present invention also relates to:
• the present invention particularly relates to an article selected from a sole of a sports shoe, a ball, a ball, gloves, personal protective equipment, a soleplate (cushion cushion) for a rail, a car part, a piece for a stroller, a wheel, a handle, a seat element, a child car seat part, a construction part, a piece of electrical and / or electronic equipment, a piece of audio equipment, sound insulation and / or thermal, a piece for damping shocks and / or vibrations, such as those generated by means of transport, wheels, smooth rolling like a tire but without the need for maintenance, and any article comprising a mixture of these articles.
• the present invention further relates to a foamable block copolymer composition comprising:
• a foaming agent comprising a hydrogencarbonate metal salt and at least one component selected from: a polycarboxylic acid containing 2 to 10 carbon atoms and at least 2 carboxyl groups,
• the foaming agent comprises an alkali metal hydrogencarbonate and citric acid or a salt thereof.
• the foamable block copolymer composition further comprises from 0.5 to 20% by weight relative to the total weight of the composition, thermoplastic capsules containing a gas and which expand under the effect of a temperature in the range of 90 to 250 ° C, said capsules having an average size D50 in the range of 8 to 20 ⁇ before expansion and an average size D50 in the range of 30 to 130 ⁇ after expansion in the foam.
• the foamable block copolymer composition according to the invention further comprises from 10 to 50% by weight of a desiccant comprising zeolite and / or alkaline earth metal oxide.
• a process for manufacturing a foam according to the invention comprising the following steps:
• the method according to the invention further comprises, especially during the heating step, the mixture of the copolymer in the molten state with the chemical foaming agent, and optionally with one or more additives.
• the method according to the invention comprises a step of injecting the composition according to the invention, that is to say the injection of the mixture of copolymer and chemical foaming agent, into a mold, the foaming of the mixture (of the composition according to the invention), at the end of its heating, being carried out:
• the method according to the invention comprises the extrusion of said foamable composition, inducing the foaming of said composition by decomposition of the foaming agent, directly at the extrusion outlet.
• the process according to the invention comprises heating said foamable composition in a reactor ("batch" process), in which a thermodynamic instability in pressure jump and / or temperature is optionally created, which generates (s) the foaming of said composition.
• a physical blowing agent is added during the mixing step, said physical expansion agent being preferably selected from nitrogen, carbon dioxide, hydrocarbons, chlorofluorocarbons, hydrochlorocarbons, hydrofluorocarbons, hydrochlorofluorocarbons, and mixtures thereof.
• Physical foaming agents such as the N 2 molecular nitrogen / carbon dioxide C0 2 / are in the form of gas. These gases are soluble in the high pressure copolymer melt. By depressurizing the system, nucleation and bubble growth generate a cellular structure.
• C0 2 in its supercritical state is used in combination with the composition according to the invention.
• the method does not use a gas injection device; and can therefore be used in existing implementation devices already used to shape block copolymers without any necessary modifications.
• 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.
• these properties are obtained over a wide temperature range, preferably from -20 ° C to 50 ° C, or even from -30 ° C to 80 ° C.
• a non-crosslinked block copolymer preferably polyamide block and polyether block, characterized by particular ranges of molecular weight, especially for polyamide blocks and polyether blocks, as well as particular range of mass ratio between the blocks, respectively between the polyamide blocks and the polyether blocks.
• the invention uses a block copolymer.
• thermoplastic elastomeric polymers which comprise, alternately, so-called hard or rigid blocks or segments (with rather thermoplastic behavior) and so-called flexible or flexible blocks or segments (with rather elastomeric behavior).
• the polyamide blocks are known to be so-called rigid segments with a melting temperature (Tf) or glass transition temperature (Tg) higher than the polymer use temperature, whereas the polyether blocks are so-called flexible segments. at Tf or Tg lower than the temperature of use of said polymer.
• a block is said to be “flexible” if it has a low glass transition temperature (Tg).
• Tg glass transition temperature
• Tg glass transition temperature
• Flexible or soft blocks that can be envisaged in the copolymer according to the invention are especially those selected from polyether blocks, polyester blocks, polysiloxane blocks, such as polydimethylsiloxane or PDMS blocks, polyolefin blocks, polycarbonate blocks, and their mixtures.
• the flexible blocks that can be envisaged are described, for example, in French Patent Application No. 0950637, page 32 line 3 to page 38 line 23.
• the polyether blocks are chosen from polyethylene glycol (PEG), poly (1,2-propylene glycol) (PPG), poly (1,3-propylene glycol) (PO3G), poly (tetramethylene glycol) (PTMG), and copolymers or mixtures thereof.
• the rigid blocks may be based on polyamide, polyurethane, polyester or a mixture of these polymers. These blocks are described in particular in the French patent application No. 0856752.
• the rigid blocks are preferably based on polyamide.
• the polyamide blocks (abbreviated PA) may comprise homopolyamides or copolyamides.
• the polyamide blocks that can be envisaged in the composition of the invention are in particular those defined in application FR0950637 of page 27 line 18 to page 31 line 14.
• said at least one block copolymer comprises at least one block chosen from: polyether blocks, polyester blocks, polyamide blocks, polyurethane blocks, and mixtures thereof.
• polyether blocks also known as COPE or copolyetheresters
• polyurethane block and polyether block copolymers also called TPU abbreviation of thermoplastic polyurethanes
• copolymers with polyamide blocks and polyether blocks also called PEBA according to IUPAC, or even polyether-block-amide.
• said at least one copolymer comprises a copolymer with polyamide blocks and polyether blocks (PEBA).
• PEBA polyether blocks
• the PEBAs result from the polycondensation of polyamide blocks with reactive ends with polyether blocks with reactive ends, such as, among others, polycondensation:
• polyether diols ⁇ , ⁇ -dihydroxy aliphatic polyoxyalkylene called polyether diols; 3) polyamide blocks with dicarboxylic chain ends with polyether diols, the products obtained being, in this particular case, polyetheresteramides.
• 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.
• 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.
• dicarboxylic acids include 1,4-cyclohexyldicarboxylic acid, butanedioic, adipic, azelaic, suberic, sebacic, dodecanedicarboxylic, octadecanedicarboxylic acids and terephthalic and isophthalic acids, but also dimerized fatty acids. .
• diamines examples 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).
• BCM bis (4-aminocyclohexyl) methane
• BMACM bis - (3-methyl-4-aminocyclohexyl) methane
• BMACP 2-2-bis-
• 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.
• PA XY X represents the number of atoms of carbon from the diamine residues
• Y represents the number of carbon atoms from the diacid residues, conventionally.
• the polyamide blocks result from the condensation of one or more ⁇ , ⁇ -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.
• lactams include caprolactam, oenantholactam and lauryllactam.
• ⁇ , ⁇ -amino carboxylic acid mention may be made of aminocaproic acid, amino-7-heptanoic acid, amino-11-undecanoic acid and amino-12-dodecanoic acid.
• the polyamide blocks of the second type are blocks of PA 11 (polyundecanamide), PA 12 (polydodecanamide) or PA 6 (polycaprolactam).
• PA 11 polyundecanamide
• PA 12 polydodecanamide
• PA 6 polycaprolactam
• PA X represents the number of carbon atoms derived from the amino acid residues.
• the polyamide blocks result from the condensation of at least one ⁇ , ⁇ -aminocarboxylic acid (or a lactam), at least one diamine and at least one dicarboxylic acid.
• polyamide PA blocks are prepared by polycondensation:
• comonomer or ⁇ Z ⁇ comonomers chosen from lactams and ⁇ , ⁇ -aminocarboxylic acids having Z carbon atoms and equimolar mixtures of at least one diamine having XI carbon atoms and at least one dicarboxylic acid having Yl carbon atoms, (XI, Yl) being different from (X, Y),
• said one or more comonomers ⁇ Z ⁇ being introduced in a proportion by weight of preferably up to 50%, preferably up to 20%, even more preferably up to 10% with respect to all the polyamide precursor monomers;
• 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.
• the polyamide blocks result from the condensation of at least two ⁇ , ⁇ -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.
• aliphatic ⁇ , ⁇ -aminocarboxylic acid mention may be made of aminocaproic, amino-7-heptanoic, amino-11-undecanoic and amino-12-dodecanoic acids.
• lactam include caprolactam, oenantholactam and lauryllactam.
• aliphatic diamines mention may be made of hexamethylenediamine, dodecamethylenediamine and trimethylhexamethylenediamine.
• cycloaliphatic diacids mention may be made of 1,4-cyclohexyldicarboxylic acid.
• aliphatic diacids mention may be made of butanedioic acid, adipic acid, azelaic acid, suberic acid, sebacic acid, dodecanedicarboxylic acid and dimerized fatty acid.
• 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 ⁇ , ⁇ -diacids .
• aromatic diacids mention may be made of terephthalic (T) and isophthalic (I) acids.
• cycloaliphatic diamines As examples of cycloaliphatic diamines, it is possible to 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-cyclohexylmethane (PACM).
• BAMN isophoronediamine
• BAMN 2,6-bis (aminomethyl) -norbornane
• piperazine Other diamines commonly used may be isophoronediamine (IPDA), 2,6-bis (aminomethyl) -norbornane (BAMN) and piperazine.
• polyamide blocks of the third type mention may be made of the following:
• PA 6.6 / 6 where 6.6 denotes hexamethylenediamine units condensed with adipic acid and 6 denotes units resulting from the condensation of caprolactam;
• 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.
• PA X / Y, PA X / Y / Z, etc. relate to copolyamides in which X, Y, Z, etc. represent homopolyamide units as described above.
• 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.
• the polyether blocks consist of alkylene oxide units.
• the polyether blocks can in particular be PEG (polyethylene glycol) blocks, that is to say constituted by ethylene oxide units, and / or PPG blocks (propylene glycol).
• PEBA copolymers may comprise in their chain several types of polyethers, the copolyethers may be block or statistical.
• the polyether blocks may also consist of ethoxylated primary amines.
• ethoxylated primary amines mention may be made of the products of formula:
• m and n are integers between 1 and 20 and x an integer between 8 and 18.
• the flexible polyether blocks may comprise polyoxyalkylene blocks with NH 2 chain ends, such blocks being obtainable by cyanoacetylation of aliphatic ⁇ , ⁇ -dihydroxylated polyoxyalkylene blocks known as polyetherdiols.
• Jeffamine or Elastamine commercial products may be used (e.g. Jeffamine® D400, D2000, ED 2003, XTJ 542, Huntsman's 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).
• 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.
• 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.
• the copolymer according to the invention may be 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 selected from copolyetheresteramides and amidetethane co-polyamines.
• PEBA copolymers in the context of the invention are: Al 2-PEG, PA-PEG, PA-6/12-PEG, PA-PEG, PA-12-PTMG, PA-PTMG, PA-6/12-PTMG, PA PTMG, Al 2-PEG / PPG, PA6-PEG / PPG, P A6 / 12-PEG / PPG, PAll-PEG / PPG, PA11 / PO3G, PA6.10 / PO3G and / or PA10.10 / PO3G.
• the foam of the invention comprises a block copolymer as described above: preferably only one such copolymer is used. However, it is possible to use a mixture of two or more block copolymers, including several PEBAs, as described above.
• the number-average molar mass of the rigid blocks, for example polyamide, in the copolymer, for example PEBA is in the range of 200 to 2000 g / mol; the number-average molar mass of the soft blocks, for example polyether, is in the range of 800 to 2500 g / mol.
• the number average molecular weight is set by the chain limiter content. It can be calculated according to the relation:
• nmonomer number of moles of monomer
• niimiter number of moles of excess diacid
• Repeat pattern Molecular weight of the pattern of repetition
• Miimiteur Molar mass of excess diacid
• the mass ratio of the rigid blocks (for example polyamide in the case of PEBA) with respect to the soft blocks (polyether in the case of PEBA) of the copolymer is from 0.1 to 2.
• This mass ratio can be calculated by dividing the average molar mass in number of the rigid blocks, in particular polyamides, by the molar mass average number of flexible blocks, especially polyethers in the case of PEBA.
• 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; or from 0.9 to 1; or from 1 to 1.1; or from 1.1 to 1.2; or 1.2 to 1.3; or from 1.3 to 1.4; or 1.4 to 1.5; or 1.5 to 1.6; or 1.6 to 1.7; or 1.7 to 1.8; or 1.8 to 1.9; or from 1.9 to 2.
• 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: 2003 standard.
• the block copolymer in particular the polyamide block and polyether block copolymer, is used to form a foam, without a crosslinking step.
• the foam according to the invention is formed by mixing the copolymer in the molten state with a chemical foaming or foaming agent and then carrying out a foaming step.
• the foam thus formed consists essentially, if not all, of the copolymer described above (or the copolymers, if a mixture of copolymers is used) and the decomposition products of the blowing agent or blowing agent. chemical foaming, which is dispersed in the matrix, rather than present in the cells of the foam.
• the block copolymer in particular with polyamide blocks and with polyether blocks, can 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 sold under the name Lotryl® by Arkema. These additives can be used to adjust the hardness of the foamed piece, its appearance and its comfort. These additives can be added in a content of 0.1 to 50% by weight, preferably 5 to 30% by weight, relative to the total weight of the composition according to the invention.
• composition according to the invention may furthermore comprise additives, such as nucleating agents, in particular mineral fillers, such as talc.
• additives such as nucleating agents, in particular mineral fillers, such as talc.
• their content is from 0.1 to 10% by weight, preferably from 0.1 to 3% by weight relative to the total weight of the composition according to the invention.
• a chemical foaming agent can be coupled with that of a physical expansion agent.
• a physical agent such as, for example, nitrogen or carbon dioxide, or a hydrocarbon, chlorofluorocarbon, hydrochlorocarbon, hydrofluorocarbon or hydrochlorofluorocarbon (saturated or unsaturated).
• a physical agent such as, for example, nitrogen or carbon dioxide, or a hydrocarbon, chlorofluorocarbon, hydrochlorocarbon, hydrofluorocarbon or hydrochlorofluorocarbon (saturated or unsaturated).
• butane or pentane may be used.
• the physical blowing agent is preferably mixed in liquid or supercritical form with the foamable copolymer composition and then converted to the gas phase during the foaming step.
• the foamable copolymer composition according to the invention is injected into a mold, and the foaming of the composition is produced either during its injection into the mold or by opening the mold.
• 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.
• the foam according to the invention has a rebound resilience, according to ISO 8307: 2007, greater than or equal to 55%.
• the foam according to the invention has a compression set, according to ISO 7214: 2012, less than or equal to 10%, and more preferably less than or equal to 8
• 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.
• 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.
• balloons can also be used to make balloons, sports gloves (eg football gloves), components of golf balls, snowshoes, protective elements (vests, inner helmet elements, cockles ... ).
• sports gloves eg football gloves
• protective elements vests, inner helmet elements, cockles ...
• the foam according to the invention has interesting anti-shock, anti-vibration and anti-noise properties, combined with haptic properties adapted to capital goods. It can also be used for the manufacture of insoles (or cushioning cushion) of railway rails, or various parts in the automobile industry, in transport, of parts for stroller, such as a wheel, a handle, an element of a seat, a child car seat part, a construction part, in electrical and electronic equipment, in audio equipment, in equipment for insulation, in particular acoustic and / or thermal insulation, in the manufacture of a part intended to cushion shocks and / or vibrations, such as those generated by a means of transport, of wheels, with a smooth rolling action such as a tire but without the need for maintenance, in construction or in the manufacturing industry .
• foam objects according to the invention can be easily recycled, for example by melting them in an extruder equipped with a degassing outlet (optionally after having cut into pieces).
• the PEBA copolymers (Pebax® from Arkema) used in the test compositions (examples and comparative) have the following characteristics summarized in the table below:
• ACM1 mixture based on citric acid and sodium hydrogencarbonate (NaHC03) (product of the Hydrocerol® range of Clariant).
• foaming agent based on metal carbonate used in the foamable composition according to the invention
• the parts obtained have a density of less than or equal to 800 kg / m3.
• the cell sizes are homogeneous: the difference between the internal diameters of the pores (or closed cells) does not exceed 30%.
• the foam obtained in Examples 1 to 6 according to the invention has a rebound resilience, according to ISO 8307: 2007, greater than 55%.
• this foam has a compression set, according to ISO 7214: 2012, less than 10%.
• the foam obtained according to the invention is characterized by its controlled and uniform structure and its mechanical properties, in particular fatigue strength and damping, compatible with use in sports, personal protective equipment, sound insulation and / or thermal, and the manufacture of parts for damping vibrations, particularly related to transport.

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• 2017
  • 2017-02-08 FR FR1751046A patent/FR3062653B1/fr active Active
• 2018
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