Classifications

• • 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
  • 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
  • C08G69/40—Polyamides containing oxygen in the form of ether groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L15/00—Compositions of rubber derivatives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L17/00—Compositions of reclaimed rubber
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L19/00—Compositions of rubbers not provided for in groups C08L7/00 - C08L17/00
  • C08L19/003—Precrosslinked rubber; Scrap rubber; Used vulcanised rubber
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/08—Copolymers of ethene
  • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
  • C08L23/0869—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen with unsaturated acids, e.g. [meth]acrylic acid; with unsaturated esters, e.g. [meth]acrylic acid esters
  • C08L23/0884—Epoxide-containing esters
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
  • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
  • B29B17/04—Disintegrating plastics, e.g. by milling
  • B29B17/0412—Disintegrating plastics, e.g. by milling to large particles, e.g. beads, granules, flakes, slices
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
  • B29K2105/26—Scrap or recycled material
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2203/00—Applications
  • C08L2203/30—Applications used for thermoforming
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2207/00—Properties characterising the ingredient of the composition
  • C08L2207/20—Recycled plastic
  • C08L2207/24—Recycled plastic recycling of old tyres and caoutchouc and addition of caoutchouc particles
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2312/00—Crosslinking
• • 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
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
  • Y02W30/00—Technologies for solid waste management
  • Y02W30/50—Reuse, recycling or recovery technologies
  • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

• composition comprising a copolymer with polyamide and polyether blocks and a crosslinked rubber powder
• the present invention relates to compositions based on copolymer with polyamide blocks and with polyether blocks and crosslinked rubber powder, in particular resulting from the grinding of used tires, as well as a process for preparing them. It also relates to articles consisting of or comprising an element consisting of or comprising such compositions, such as shoe soles, their method of preparation, and their method of recycling. It also relates to the granules, filaments or powders obtained by this recycling process as well as the articles prepared from them.
• Polymer compositions used in the field of sports equipment such as soles or sole components, gloves, rackets or golf balls, or individual protection elements in particular for the practice of sport (vests, inner parts of helmets , shells, etc.) must meet many requirements, particularly in terms of rebound ability, low residual deformation in traction and ability to withstand repeated impacts and return to the initial shape.
• Document WO17021164 describes a composition comprising rubber powder, thermoplastic polyurethanes obtained from a polyisocyanate and a polyol, as well as a polysiloxane. This composition can in particular be used to absorb shocks in a shoe sole.
• the present invention relates firstly to a composition comprising, relative to the total weight of the composition:
• compatibilizing agents • from 0 to 40% of compatibilizing agents, preferably from 5 to 20%, in particular from 10 to 15%.
• the crosslinked rubber powder has a specific surface of between 0.01 m 2 /g and 100 m 2 /g; the crosslinked rubber powder has a median diameter D50 of between 2 and 500 ⁇ m, preferably between 50 and 300 ⁇ m; the diameter D90 of the crosslinked rubber powder is between 10 and 800 ⁇ m, preferably between 80 and 500 ⁇ m, and more preferably between 100 and 300 ⁇ m; the rubber of the crosslinked rubber powder is a natural or synthetic rubber or a mixture thereof; the rubber of the crosslinked rubber powder contains 0 to 50% by weight, preferably 5 to 40% by weight of a synthetic rubber or a mixture of synthetic rubbers; the rubber of the crosslinked rubber powder contains 10 to 80% by weight, preferably 15 to 70% by weight of natural rubber; the natural rubber is cis-1,4-polyisoprene or trans-1,4-polyisoprene; the crosslinked rubber powder comprises styrene and butadiene rubber, preferably in a content greater than 5% by
• the invention also relates to a method for preparing a composition according to the invention, comprising the following steps:
• the mixture preferably in an extruder, o from 20 to 90% by weight, preferably from 40 to 70%, by weight, of at least one copolymer with polyamide blocks and with polyether blocks, in the molten state and o from 10 to 80%, preferably from 30 to 60%, by weight, of at least one crosslinked rubber powder, in particular from used tires, o from 0 to 5% of additives, preferably from 0.1 to 4%, in particular from 1 to 2%; o from 0 to 40% of compatibilizing agents, preferably from 5 to 20%, in particular from 10 to 15%, • optionally, shaping the mixture in the form of granules, filaments or powder, and/or
• the invention also relates to an article consisting of, or comprising, at least one element consisting of or comprising, a composition according to the invention, said article preferably being chosen from footwear components such as soles, ski pole parts, racket and golf club handles, goalie gloves, treadmills, aquatic equipment such as diving shoes, mask and snorkel parts, eyeglass frame parts (sleeve, temples, nose pads), frames for ski goggles, parts providing vibration isolation in electronics and machinery, shells for external batteries, automotive parts (seals, tips), toys, watch straps, buttons on machinery, seals, or conveyor belt components.
• footwear components such as soles, ski pole parts, racket and golf club handles, goalie gloves, treadmills, aquatic equipment such as diving shoes, mask and snorkel parts, eyeglass frame parts (sleeve, temples, nose pads), frames for ski goggles, parts providing vibration isolation in electronics and machinery, shells for external batteries, automotive parts (seals, tips), toys, watch straps, buttons on machinery, seals, or conveyor belt components.
• the invention also relates to a method of manufacturing an article according to claim 18, comprising the steps of:
• the invention also relates to a process for recycling an article according to the invention comprising the following successive steps: a) recovery, after optional separation, of at least part of said article made of thermoplastic material comprising a composition according to the invention; b) grinding the thermoplastic material to obtain particles, c) melting the particles to obtain a molten mixture, and d) optionally, adding other components to the molten mixture, e) optionally, forming granules, filaments or powders from the molten mixture obtained at the end of step c) or d), and f) optionally, shaping of the granules, filaments or powders.
• the invention also relates to a granule, filament or powder capable of being obtained according to the recycling process according to the invention.
• the invention also relates to an article consisting of or comprising at least one element prepared from granules, filaments or powders according to the invention.
• the present invention makes it possible to meet the need expressed above. More particularly, it provides a composition having good resistance to abrasion, good anti-slip properties (estimated using the coefficient of friction), and good tensile properties.
• This composition has in particular good springback, low density, high elongation at break, good adhesion to wet surfaces and is recyclable due to its fusible nature.
• compositions of the state of the art were able to observe that these compositions exhibited a lower tangent delta than that of the compositions of the state of the art. This characteristic is particularly advantageous for use in sports shoe soles since less energy is dissipated via the compositions, which allows the runner to run faster.
• the invention relates to a composition comprising, relative to the total weight of the composition:
• the crosslinked rubber powder used in the compositions of the invention can be characterized by a particular specific surface.
• the specific surface of the crosslinked rubber powder is between 0.01 m 2 /g and 100 m 2 /g, in particular between 0.01 m 2 /g and 80 m 2 /g, in particular between 0.01 m 2 /g and 50 m 2 /g and very particularly between 0.01 and 10 m 2 /g, advantageously between 0.03 m 2 /g and 0.50 m 2 /g.
• the specific surface is between 0.01 and 0.50 m 2 /g, in particular between 0.05 m 2 /g to 0.30 m 2 /g, preferably between 0.08 m 2 /g to 0.20 m 2 /g and more preferably between 0.1 and 0.2 m 2 /g.
• This specific surface is measured by the BET method as described in Shen et al. construction Build. Mater. 2009, 23 (1), 304-310.
• the crosslinked rubber powder preferably has a particular particle size, in particular a specific D50, D90 and/or D10 diameter characterizing the size distribution of the crosslinked rubber particles.
• the crosslinked rubber powder preferably has a median diameter D50 of between 2 and 500 ⁇ m, preferably between 50 and 300 ⁇ m, and more preferably between 60 and 200 ⁇ m.
• the diameter D90 of the powder can in particular be between 10 and 800 ⁇ m, preferably between 80 and 500 ⁇ m, and more preferably between 100 and 300 ⁇ m.
• the diameter D10 of the powder can in particular be comprised from 1 to 300 ⁇ m, preferably from 5 to 200 ⁇ m, and more preferentially from 10 to 100 ⁇ m.
• diameter or "D” of the powder is understood to mean the average diameter by mass of a powder material, as measured according to the "Rotap sieve tests” method using machines such as the RX- 94 Duo or the RO-TAP Premium marketed by W.S. Tyler, equipped with sieves complying with the ISO 3310-1:2016 standard.
• the D50 designates the median diameter by mass, respectively the diameters below which 50% by mass of the particles are located. Additionally, the D10 and D90 respectively designate the diameters below which 10 or 90% by mass of the particles are located.
• crosslinked rubber is meant, within the meaning of the present description, a crosslinked natural rubber and/or a crosslinked synthetic rubber (elastomer).
• the rubber used in the manufacture of crosslinked rubber powder can be virtually any type of sulfur vulcanized rubber compound and can come from a wide variety of sources.
• the rubber of the crosslinked rubber powder may contain from 0 to 50% by weight, preferably from 5 to 40% by weight of a synthetic rubber or a mixture of synthetic rubbers.
• the rubber of the crosslinked rubber powder may contain 10 to 80% by weight, preferably 15 to 70% by weight of natural rubber.
• the natural rubber may in particular be chosen from cis-1,4-polyisoprene or trans-1,4-polyisoprene.
• the rubber of the cross-linked rubber powder may contain styrene and butadiene rubber, preferably in a content greater than 5% by weight, more preferably greater than 10% by weight.
• Cross-linked rubber powder can come from various sources, including the recycling of industrial waste or finished objects after use. Such objects can come from many fields such as in clothing, in particular the outer soles of shoes and boots; in the automobile, sealing parts such as seals, airbags, floor mats, anti-vibration mounts and fittings; in industry, bands conveyors, belts, potable water seals, O-rings, cables and hoses.
• window seals, foam mattresses, golf balls, tennis balls, windsurfing suits, masks and flippers in building, anti-seismic bridges and blocks, flexible tanks and sections; in hygiene and medicine: gloves and bottle teats.
• Cross-linked rubber powder comes from the recycling of used products. These may include used tires, at the end of their life and/or having driven at least 20 km. Recycled crosslinked rubber, in particular from used tires, may comprise functions produced during thermo-oxidation reactions in a higher content than that observed in virgin rubber from any use. These functions can in particular be phenylhydrazone, carbonyl such as ketones, hydroxyl or sulfenic acid, advantageously carbonyl and sulfenic acid functions.
• these polar functions could make it possible to improve the interactions between the matrix based on thermoplastic PEBA, and the particles of crosslinked rubber powder and thus the physical properties of the composite material.
• An example of a source of cross-linked rubber powder from used tires is the rubber compound recovered during the polishing of vehicle tire treads, as part of regrooving procedures.
• rubber can come from a wide variety of sources, including whole tires, tire sidewalls, inner tire liners, tire carcasses, power transmission belts, belts conveyor belts, hoses and a wide variety of other rubber products.
• the crosslinked rubber powder used in accordance with the present description is typically a powder of a mixture of natural rubber and synthetic rubber such as polyisoprene synthetic rubber, polybutadiene rubber and styrene-butadiene rubber.
• the crosslinked rubber powder implemented according to the invention can be a mixture of two or more of these rubbers or it can be composed of a single type of rubber.
• powder Crosslinked rubber may be comprised solely of natural rubber, synthetic polyisoprene rubber, styrene-butadiene rubber, a mixture of natural rubber and polybutadiene rubber, or a mixture of natural rubber and styrene-butadiene rubber.
• Cross-linked rubber powder can be prepared by different methods.
• rubber powder can be obtained by a grinding process.
• Different grinding processes exist such as, for example, mechanical grinding at room temperature, cryogenic grinding, grinding using water jets, or powder micronization.
• Waterjet grinding also known as waterjet cutting, is particularly preferred for used tires.
• the crosslinked rubber powder may contain from 1 to 70%, preferably from 5 to 50%, more preferably from 10 to 40% of carbon black and/or silica.
• the crosslinked rubber powder includes carbon black and silica.
• the silica content is twice, very advantageously 5 times, higher than the carbon black content, the content representing the content by weight relative to the total weight of the composition.
• the crosslinked rubber powder may comprise less than 10%, advantageously less than 5%, very advantageously less than 1% of fibrous material.
• the composition does not include fiberglass.
• the crosslinked rubber powder may contain 0.05 to 5% by weight, preferably 0.1% to 2.5% by weight of zinc oxide.
• PEBAs result from the polycondensation of polyamide blocks (rigid or hard blocks) with reactive ends with polyether blocks (soft or soft blocks) with reactive ends, such as, among others, polycondensation:
• polyamide blocks with diamine chain ends with polyoxyalkylene blocks with dicarboxylic chain ends 1) polyamide blocks with ends of dicarboxylic chains with polyetherdiols (aliphatic polyoxyalkylene a,oo-dihydroxylated blocks), 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 36 carbon atoms, preferably those having from 4 to 20 carbon atoms, more preferably from 6 to 18 carbon atoms. carbon, and an aliphatic or aromatic diamine, in particular those having 2 to 20 carbon atoms, preferably those having 6 to 14 carbon atoms.
• a dicarboxylic acid in particular those having from 4 to 36 carbon atoms, preferably those having from 4 to 20 carbon atoms, more preferably from 6 to 18 carbon atoms. carbon
• an aliphatic or aromatic diamine in particular those having 2 to 20 carbon atoms, preferably those having 6 to 14 carbon atoms.
• dicarboxylic acids mention may be made of 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 tetramethylene diamine, hexamethylenediamine, 1,10-decamethylenediamine, dodecamethylenediamine, trimethylhexamethylenediamine, isomers of bis-(4-aminocyclohexyl)-methane (BACM), bis -(3-methyl-4- aminocyclohexyl)methane (BMACM), and 2-2-bis-(3-methyl-4- aminocyclohexyl)-propane (BMACP), paraamino-di-cyclo-hexyl-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-
• 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 carbon atoms resulting from the diamine residues
• Y represents the number of carbon atoms resulting from the diacid residues, in a conventional manner.
• the polyamide blocks result from the condensation of one or more a,oo-aminocarboxylic acids and/or of one or more lactams having from 6 to 12 carbon atoms in the presence of a dicarboxylic acid having from 4 with 18 carbon atoms or a diamine.
• lactams mention may be made of caprolactam, oenantholactam and lauryllactam.
• ⁇ , ⁇ -amino carboxylic acid mention may be made of aminocaproic, amino-7-heptanoic, amino-10-decanoic, amino-11-undecanoic and amino-12-dodecanoic.
• the polyamide blocks of the second type are blocks of PA 10 (polydecanamide), PA 11 (polyundecanamide), of PA 12 (polydodecanamide) or of PA 6 (polycaprolactam).
• PA X notation X represents the number of carbon atoms from 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:
• said ⁇ Z ⁇ comonomer(s) being introduced in a proportion by weight advantageously ranging up to 50%, preferably up to 20%, even more advantageously up to 10% relative to all of the polyamide precursor monomers;
• the polyamide blocks result from the condensation of at least two a,oo-aminocarboxylic acids or of at least two lactams having from 6 to 12 carbon atoms or of a lactam and of a aminocarboxylic acid not having the same number of carbon atoms in the optional presence of a chain limiter.
• aliphatic ⁇ ,oo-aminocarboxylic acid of aminocaproic, amino-7-heptanoic, amino-10-decanoic, amino-11-undecanoic and amino-12-dodecanoic acids.
• lactam mention may be made of caprolactam, oenantholactam and lauryllactam.
• aliphatic diamines include hexamethylenediamine, dodecamethylenediamine and trimethylhexamethylenediamine.
• cycloaliphatic diacids mention may be made of 1,4-cyclohexyldicarboxylic acid.
• aliphatic diacids mention may be made of butane-dioic, adipic, azelaic, suberic, sebacic, dodecanedicarboxylic acids, dimerized fatty acids.
• dimerized fatty acids preferably have a dimer content of at least 98%; preferably they are hydrogenated; these are, for example, products marketed under the "PRIPOL” brand by the "CRODA” company, or under the EMPOL brand by the BASF company, or under the Radiacid brand by the OLEON company, and polyoxyalkylene a,oo-diacids .
• aromatic diacids mention may be made of terephthalic (T) and isophthalic (I) acids.
• cycloaliphatic diamines examples include 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 paraamino-di-cyclo-hexyl-methane (PACM).
• BMACM bis-(4-aminocyclohexyl)-methane
• BMACM bis-(3-methyl-4-aminocyclohexyl)methane
• BMACP 2-2-bis- (3-methyl-4-aminocyclohexyl)-propane
• PAM paraamino-di-cyclo-hexyl-methane
• IPDA isophoronediamine
• BAMN 2,6-bis-(aminomethyl)-norbornane
• polyamide blocks of the third type By way of examples of polyamide blocks of the third type, the following may be mentioned: - PA 6.6/6, or 6.6 designated hexamethylenediamm units condensed with adipic acid and 6 designates units resulting from the condensation of caprolactam;
• PA X/Y, PA X/Y/Z, etc. refer 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 10, 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 6.6, 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 thereof; and preferably comprise blocks of polyamide PA 6, PA 10, PA 11, PA 12, PA 6.10, PA 6.12, PA 10.10, PA 10.12, or mixtures or copolymers thereof, more preferably blocks of polyamide PA 11 , PA 12, PA 6, PA 6.12,
• the polyether blocks consist of alkylene oxide units.
• the polyether blocks can in particular be PEG (polyethylene glycol) blocks, i.e. consisting of ethylene oxide units, and/or PPG (propylene glycol) blocks, i.e. consisting of propylene oxide units, and/or PO3G (polytrimethylene glycol) blocks, that is to say consisting of polytrimethylene glycol ether units, and/or PTMG blocks, that is to say consisting of tetramethylene glycol units also called polytetrahydrofuran.
• the PEBA copolymers can comprise in their chain several types of polyethers, the copolyethers possibly being block or random. 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 can also consist of ethoxylated primary amines.
• 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 brand NORAMOX® from the company CECA and under the brand GENAMIN® from the company CLARIFYING.
• the polyetherdiol blocks are copolycondensed with polyamide blocks with carboxylic ends.
• the general two-step method for preparing PEBA copolymers having ester bonds between the PA blocks and the PE blocks is known and is described, for example, in document FR 2846332.
• the general method for preparing PEBA copolymers having amide bonds between the PA blocks and the PE blocks is known and described, for example in document EP 1482011.
• the polyether blocks can also be mixed with polyamide precursors and a diacid chain limiter to prepare polymers with polyamide blocks and polyether blocks. polyethers having randomly distributed units (one-step process).
• the PEBA can comprise ends of amine chains, provided that it comprises ends of OH chains.
• PEBAs comprising amine chain ends can result from the polycondensation of polyamide blocks with dicarboxylic chain ends with polyoxyalkylene blocks with diamine chain ends, obtained for example by cyanoethylation and hydrogenation of polyoxyalkylene a,oo-dihydroxylated aliphatic blocks called polyetherdiols.
• PEBA in the present description of the invention relates both to PEBAX® marketed by Arkema, to Vestamid® marketed by Evonik, to Grilamid® marketed by EMS, and to Pelestat® type PEBA marketed by Sanyo or to any other PEBA from other providers.
• block copolymers described above generally comprise at least one polyamide block and at least one polyether block
• the present invention also covers copolymers comprising two, three, four (or even more) different blocks chosen from those described in the present description. , provided that these blocks comprise at least polyamide and polyether blocks.
• the copolymer can be a segmented block copolymer comprising three different types of blocks (or "triblock"), which results from the condensation of several of the blocks described above.
• Said triblock can for example be a copolymer comprising a polyamide block, a polyester block and a polyether block or a copolymer comprising a polyamide block and two different polyether blocks, for example a PEG block and a PTMG block.
• the triblock is preferably a copolyetheresteramide.
• PEBA copolymers in the context of the invention are copolymers comprising blocks: PA 10 and PEG; PA 10 and PTMG; PA 11 and PEG; PA 11 and PTMG; PA12 and PEG; PA 12 and PTMG; PA 6.10 and PEG; PA 6.10 and PTMG; PA 6 and PEG; PA 6 and PTMG; PA 6.12 and PEG; PA 6.12 and PTMG.
• the number-average molar mass of the polyamide blocks in the PEBA copolymer is preferably from 400 to 20,000 g/mol, more preferably from 500 to 10,000 g/mol.
• the number-average molar mass of the polyamide blocks in the PEBA copolymer is from 400 to 500 g/mol, or 500 to 600 g/mol, or from 600 to 1000 g/mol, or from 1000 to 1500 g/mol, or from 1500 to 2000 g/mol, or from 2000 to 2500 g/mol, or from 2500 to 3000 g/mol, or from 3000 to 3500 g/mol, or from 3500 to 4000 g/mol, or from 4000 to 5000 g/mol, or from 5000 to 6000 g/mol, or from 6000 to 7000 g/mol, or from 7000 to 8000 g/mol, or from 8000 to 9000 g/mol, or from 9000 to 10000 g /mol, or from 10000 to 11000 g/mol, or from
• the number-average molar mass of the polyether blocks is preferably from 100 to 6000 g/mol, more preferably from 200 to 3000 g/mol. In some embodiments, the number average molar mass of the polyether blocks is from 100 to 200 g/mol, or from 200 to 500 g/mol, or from 500 to 800 g/mol, or from 800 to 1000 g/mol , or from 1000 to 1500 g/mol, or from 1500 to 2000 g/mol, or from 2000 to 2500 g/mol, or from 2500 to 3000 g/mol, or from 3000 to 3500 g/mol, or from 3500 to 4000 g/mol, or from 4000 to 4500 g/mol, or from 4500 to 5000 g/mol, or from 5000 to 5500 g/mol, or from 5500 to 6000 g/mol.
• the number-average molar mass is fixed by the content of chain limiter. It can be calculated according to the relationship:
• n monomer represents the number of moles of monomer
• ni chain-limiter represents the number of moles of excess diacid limiter
• MWrepeat unit represents the molar mass of the repeating unit
• MWichain-limiter represents the molar mass of the excess diacid.
• the number-average molar mass of the polyamide blocks and of the polyether blocks can be measured before the copolymerization of the blocks by gel permeation chromatography (GPC).
• the mass ratio of the polyamide blocks relative to the polyether blocks of the copolymer is from 0.1 to 20, preferably from 0.5 to 18, even more preferentially from 0.6 to 15.
• This mass ratio can be calculated by dividing the number-average molar mass of the polyamide blocks by the number-average molar mass of the polyether blocks.
• the mass ratio of the polyamide blocks relative to the polyether blocks of the copolymer can be from 0.1 to 0.2, or from 0.2 to 0.3, or from 0.3 to 0.4, or from 0 .4 to 0.5, or 0.5 to 0.6, or 0.6 to 0.7, or 0.7 to 0.8, or 0.8 to 0.9, or 0 .9 to 1, or 1 to 1.5, or 1.5 to 2, or 2 to 2.5, or 2.5 to 3, or 3 to 3.5, or 3.5 to 4, or from 4 to 4.5, or from 4.5 to 5, or from 5 to 5.5, or from 5.5 to 6, or from 6 to 6.5, or from 6.5 to 7, or from 7 to 7.5, or from 7.5 to 8, or from 8 to 8.5, or from 8.5 to 9, or 9 to 9.5, or 9.5 to 10, or 10 to 11, or 11 to 12, or 12 to 13, or 13 to 14, or 14 to 15, or 15 to 16, or 16 to 17, or 17 to 18, or 18 to 19, or 19 to 20.
• the copolymer with polyamide blocks and with polyether blocks has a Shore D hardness greater than or equal to 30.
• the at least one copolymer used in the invention has an instantaneous Shore hardness of between 10D and 70D, of preferably between 25D and 50D. Hardness measurements can be performed according to ISO 7619-1.
• the PEBA according to the invention has an OH function concentration of 0.002 meq/g to 0.2 meq/g, preferably of 0.005 meq/g to 0.1 meq/g, more preferably of 0.01 meq /g to 0.08 meq/g and/or a COOH function concentration of 0.002 meq/g to 0.2 meq/g, preferably of 0.005 meq/g to 0.1 meq/g, more preferably of 0 .01 meq/g to 0.08 meq/g.
• the PEBA according to the invention may have an OH function concentration of 0.002 to 0.005 meq/g, or 0.005 to 0.01 meq/g, or 0.01 to 0.02 meq/g, or 0.02 to 0.03 meq/g, or 0.03 to 0.04 meq/g, or 0.04 to 0.05 meq/g, or 0.05 to 0.06 meq/g, or 0.06 to 0.07 meq/g, or 0.07 to 0.08 meq/g, or 0.08 to 0.09 meq/g, or 0.09 to 0.1 meq/ g, or from 0.1 to 0.15 meq/g, or from
• 0.15 to 0.2 meq/g and/or have a COOH concentration of 0.002 to 0.005 meq/g, or 0.005 to 0.01 meq/g, or 0.01 to 0.02 meq/ g, or 0.02 to 0.03 meq/g, or 0.03 to 0.04 meq/g, or 0.04 to 0.05 meq/g, or 0.05 to 0.06 meq/g, or 0.06 to 0.07 meq/g, or 0.07 to 0.08 meq/g, or 0.08 to 0.09 meq/g, or 0.09 to 0 .1 meq/g, or 0.1 to 0.15 meq/g, or 0.15 to 0.2 meq/g.
• the COOH function concentration can be determined by potentiometric analysis and the OH function concentration can be determined by proton NMR. Measurement protocols are detailed in the article "Synthesis and characterization of poly(copolyethers-block-polyamides) - IL Characterization and properties of the multiblock copolymers", Maréchal et al., Polymer, Volume 41, 2000, 3561-3580.
• the polyamide blocks of the copolymer with polyamide blocks and with polyether blocks are blocks of polyamide 11, of polyamide 12, of polyamide 10, of polyamide 6, of polyamide 6.10, of polyamide 6.12, of polyamide 10.10 and/or polyamide 10.12, preferably polyamide 11, polyamide 12, polyamide 6 and/or polyamide 6.12; and/or the polyether blocks of the copolymer containing polyamide blocks and containing polyether blocks are blocks of polyethylene glycol and/or of polytetrahydrofuran.
• the composition further comprises from 0 to 5% by weight, preferably from 0.1 to 2% by weight of additives relative to the total weight of the composition.
• the additive may be chosen in particular from a catalyst, an antioxidant, a heat stabilizer, a UV stabilizer, a light stabilizer, a lubricant, a flame retardant, a nucleating agent, a chain extender and a colorant.
• the composition comprises from 0 to 5%, 5 to 10%, from 10 to 15%, from 15 to 20%, from 20 to 25%, from 25 to 30%, from 30 to 35% or from 25 to 40% by weight of compatibilizing agents relative to the total weight of the composition.
• the presence of a compatibilizing agent can be advantageous in order to obtain a good dispersion of the crosslinked rubber powder particles within the PEBA copolymer matrix.
• ком ⁇ онент an agent making it possible to promote the compatibilization of the PEBA copolymer matrix and of the crosslinked rubber particles. They may in particular be molecules, macromolecules, polymers or copolymers having a good affinity both with the PEBA copolymer matrix and the crosslinked rubber powder, thus capable of promoting physical cohesion between the various constituents of the composition or to form a chemical bond with the matrix and/or the powder.
• the physical cohesion can result for example from a coating of the crosslinked rubber particles, from an entanglement of the polymer and/or copolymer chains and/or from Van Der Vaals or hydrogen bonds between all or part of the constituents of the composition.
• the compatibilizing agent is bound, at least partially, by a covalent bond to the matrix and/or to the rubber powder.
• the groups linking the compatibilizing agent to the matrix and/or to the powder can be urea, urethane, amide, ester or alkoxysilane groups.
• At least a part of the polyamide block and polyether block copolymer is covalently bonded to at least a part of the thermoplastic polyurethane by a urethane function, preferably an amount less than or equal to 10% by weight, more preferably less than or equal to 5% by weight, of the copolymer with polyamide blocks and with polyether blocks is covalently bonded to at least part of the thermoplastic polyurethane by a urethane function.
• the compatibilizing agent advantageously carries reactive functions which can preferably react with the alcohol, amine or carboxylic acid functions carried by the thermoplastic elastomer.
• composition according to the invention may comprise one or more compatibilizing agents chosen from copolyamides, compounds known as impact modifiers, thermoplastic polyurethanes (TPU), polymers containing silane groups, siloxanes, or a mixture thereof.
• compatibilizing agents chosen from copolyamides, compounds known as impact modifiers, thermoplastic polyurethanes (TPU), polymers containing silane groups, siloxanes, or a mixture thereof.
• the compatibilizers can be chosen from copolyamides.
• the copolyamide may in particular be of formula X/YZ or the units YZ/Y2Z2,
• X being an aliphatic a,oo-aminocarboxylic acid or a lactam having a carbon number of 6 to 18, advantageously of 6 to 12
• Y and Y2 being a diamine having a carbon number from 2 to 48, advantageously from 2 to 36
• Z and Z2 being a dicarboxylic acid having a carbon number from 6 to 48, advantageously from 6 to 36.
• the copolyamide comprises fatty acid dimer having a carbon number of 18 to 48, preferably 36 to 48.
• the compatibilizing agents can be chosen from impact modifiers, functionalized or not.
• impact modifier we mean a polymer with a lower modulus than that of the resin, exhibiting good adhesion with the matrix, so as to dissipate the cracking energy.
• the impact modifier is advantageously a polymer having a flexural modulus of less than 100 MPa (as measured according to the ISO 178 standard) and a Tg of less than 0° C. (as measured according to the 11357-2 standard at the point of inflection of the DSC thermogram), in particular a polyolefin.
• the polyolefin of the impact modifier can be functionalized or non-functionalized, or be a mixture of at least one functionalized and/or at least one non-functionalized.
• the polyolefin has been designated by (B) and functionalized polyolefins (B1) and non-functionalized polyolefins (B2) have been described below.
• a non-functionalized polyolefin (B2) is conventionally a homopolymer or copolymer of alpha olefins or diolefins, such as, for example, ethylene, propylene, butene-1, octene-1, butadiene.
• alpha olefins or diolefins such as, for example, ethylene, propylene, butene-1, octene-1, butadiene.
• LDPE low density polyethylene
• HDPE linear low density polyethylene
• LLDPE linear low density polyethylene, or linear low density polyethylene
• VLDPE very low density polyethylene, or very low density polyethylene
• metallocene polyethylene metallocene polyethylene
• ethylene/alpha-olefin copolymers such as ethylene/propylene, EPR (abbreviation of ethylene-propylene-rubber) and ethylene/propylene/diene (EPDM); styrene/ethylene-butene/styrene (SEBS), styrene/butadiene/styrene (SBS), styrene/isoprene/styrene (SIS), styrene/ethylene-propylene/styrene (SEPS) block copolymers;
• EPR abbreviation of ethylene-propylene-rubber
• EPDM ethylene/propylene/diene
• SEBS styrene/ethylene-butene/styrene
• SBS styrene/butadiene/styrene
• SIS styrene/isoprene/styrene
• SEPS styrene/
• the functionalized polyolefin (B1) can be a polymer of alpha olefins having reactive units (the functionalities); such reactive units may in particular be acid, anhydride or epoxy functions.
• reactive units may in particular be acid, anhydride or epoxy functions.
• a functionalized polyolefin is, for example, a PE/EPR mixture, the weight ratio of which can vary widely, for example from 40/60 to 90/10, said mixture being co-grafted with an anhydride, in particular maleic anhydride, according to a degree of grafting for example from 0.01 to 5% by weight, advantageously from 2.8 to 5% by weight.
• the functionalized polyolefin (B1) can be chosen from the following (co)polymers, grafted with maleic anhydride or glycidyl methacrylate, in which the degree of grafting is for example from 0.01 to 5% by weight:
• ethylene/alpha-olefin copolymers such as ethylene/propylene, EPR (abbreviation of ethylene-propylene-rubber) and ethylene/propylene/diene (EPDM).
• EPR abbreviation of ethylene-propylene-rubber
• EPDM ethylene/propylene/diene
• SEBS styrene/ethylene-butene/styrene
• SBS styrene/butadiene/styrene
• SIS styrene/isoprene/styrene
• SEPS styrene/ethylene-propylene/styrene
• alkyl (meth)acrylate copolymers containing up to 40% by weight of alkyl (meth)acrylate;
• the functionalized polyolefin (B1) can also be chosen from ethylene/propylene copolymers with a majority of propylene grafted with maleic anhydride then condensed with monoamine polyamide (or a polyamide oligomer) (products described in EP-A-20 0342066 ).
• the functionalized polyolefin (B1) can also be a co- or ter-polymer of at least the following units: (1) ethylene, (2) alkyl (meth)acrylate or saturated carboxylic acid vinyl ester and (3) anhydride such as maleic anhydride or (meth)acrylic acid or epoxy such as glycidyl (meth)acrylate.
• the (meth)acrylic acid can be salified with Zn or Li.
• alkyl (meth)acrylate in (B1) or (B2) denotes C1 to C8 alkyl methacrylates and acrylates, and can be chosen from methyl acrylate, ethyl acrylate , n-butyl acrylate, isobutyl acrylate, ethyl-2-hexyl acrylate, cyclohexyl acrylate, methyl methacrylate and ethyl methacrylate.
• the aforementioned polyolefins (B1) can also be crosslinked by any appropriate process or agent (diepoxy, diacid, peroxide, etc.); the term functionalized polyolefin also includes mixtures of the aforementioned polyolefins with a difunctional reagent such as diacid, dianhydride, diepoxy, etc. capable of reacting with these or mixtures of at least two functionalized polyolefins capable of reacting with one another.
• the copolymers mentioned above, (B1) and (B2) can be randomly or block copolymerized and have a linear or branched structure.
• MFI Melt Flow Index
• ASTM 1238 or ISO 1133:2011 standard The molecular weight, the MFI index, the density of these polyolefins can also vary to a large extent, which those skilled in the art will appreciate.
• MFI short for Melt Flow Index, is the Melt Flow Index. It is measured according to the ASTM 1238 or ISO 1133:2011 standard.
• the non-functionalized polyolefins (B2) are chosen from polypropylene homopolymers or copolymers and any homopolymer of ethylene or copolymer of ethylene and a comonomer of the higher alpha olefinic type such as butene, hexene, octene or 4-methyl 1-pentene. Mention may be made, for example, of PP, high-density PE, medium-density PE, linear low-density PE, low-density PE, very low-density PE.
• polyethylenes are known to those skilled in the art as being produced according to a “radical” process, according to a “Ziegler” type catalysis or, more recently, according to a so-called “metallocene” catalysis.
• the functionalized polyolefins (B1) are chosen from any polymer comprising alpha-olefin units and units carrying polar reactive functions such as epoxy, carboxylic acid or carboxylic acid anhydride functions.
• polymers examples include terpolymers of ethylene, alkyl acrylate and maleic anhydride or glycidyl methacrylate such as Lotader® from SK Global Chemical or polyolefins grafted with maleic anhydride such as Orevac® from SK Global Chemical as well as terpolymers of ethylene, alkyl acrylate and (meth)acrylic acid. Mention may also be made of polypropylene homopolymers or copolymers grafted with a carboxylic acid anhydride and then condensed with polyamides or monoamino polyamide oligomers.
• the impact modifier is a functionalized polyolefin (B1) bearing maleic anhydride or epoxide functions.
• the compatibilizers can be chosen from thermoplastic polyurethanes (TPU).
• TPU thermoplastic polyurethanes
• Thermoplastic polyurethane is a copolymer with rigid blocks and flexible blocks.
• Thermoplastic polyurethanes result from the reaction of at least one polyisocyanate with at least one isocyanate-reactive compound, preferably having two isocyanate-reactive functional groups, more preferably a polyol, and optionally with a chain extender, optionally in the presence of a catalyst.
• the rigid blocks of TPU are blocks made up of units derived from polyisocyanates and chain extenders while the flexible blocks mainly comprise units derived from compounds reactive with isocyanate having a molar mass between 0.5 and 100 kg/ mol, preferably polyols.
• the polyisocyanate can be aliphatic, cycloaliphatic, araliphatic and/or aromatic.
• the polyisocyanate is a diisocyanate.
• the polyisocyanate is chosen from the group consisting of tri-, tetra-, penta-, hexa-, hepta- and/or octamethylene diisocyanate, 2-methyl-pentamethylene 1,5-diisocyanate, 2-ethyl- butylene-1,4-diisocyanate, 1,5-pentamethylene diisocyanate, 1,4-butylene-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (isophorone diisocyanate, IPDI), 1,4-bis(isocyanatomethyl)cyclohexane, 1,3-bis(isocyanatomethyl)cyclohexane (HXDI), 2,4-paraphenylene diisocyanate (PPDI), 2,4-tetramethylene xylene diisocyanate (TMXDI), 4 ,4'-, 2,4'-,
• the polyisocyanate is chosen from the group consisting of diphenylmethane diisocyanates (MDI), toluene diisocyanates (TDI), pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), methylene bis (4-cyclohexyl isocyanate) (HMDI) and mixtures thereof.
• MDI diphenylmethane diisocyanates
• TDI toluene diisocyanates
• PDI pentamethylene diisocyanate
• HDI hexamethylene diisocyanate
• HMDI methylene bis (4-cyclohexyl isocyanate
• the polyisocyanate is 4,4'-MDI (4,4'-diphenylmethane diisocyanate), 1,6-HDI (1,6-hexamethylene diisocyanate) or a mixture of these.
• the compound(s) reactive with the isocyanate preferably have an average functionality between 1.8 and 3, more preferably between 1.8 and 2.6, more preferably between 1.8 and 2.2.
• the average functionality of the compound(s) reactive with the isocyanate corresponds to the number of functions reactive with the isocyanate of the molecules, calculated theoretically for a molecule from a quantity of compounds.
• the compound reactive with the isocyanate has, according to a statistical average, a Zerewitinoff active hydrogen number in the above ranges.
• the compound reactive with the isocyanate (preferably a polyol) has a number average molar mass of 500 to 100,000 g/mol.
• the compound reactive with the isocyanate can have a number-average molar mass of 500 to 8000 g/mol, more preferably from 700 to 6000 g/mol, more particularly from 800 to 4000 g/mol.
• the isocyanate-reactive compound has a number average molecular weight of 500 to 600 g/mol, or 600 to 700 g/mol, or 700 to 800 g/mol, or 800 to 1000 g/mol, or 1000 to 1500 g/mol, or 1500 to 2000 g/mol, or 2000 to 2500 g/mol, or 2500 to 3000 g/mol, or 3000 to 3500 g/mol, or from 3500 to 4000 g/mol, or from 4000 to 5000 g/mol, or from 5000 to 6000 g/mol, or from 6000 to 7000 g/mol, or from 7000 to 8000 g/mol, or from 8000 to 10000 g/mol, or from 10000 to 15000 g/mol, or from 15000 to 20000 g/mol, or from 20000 to 30000 g/mol, or from 30000 to 40000 g/mol, or from 40000 to 50000 g/mol, or from 50,000 to 60,000 g/mol, or from
• the isocyanate-reactive compound has at least one reactive group selected from hydroxyl group, amine group, thiol group and carboxylic acid group.
• the compound reactive with The isocyanate has at least one reactive hydroxyl group, more preferably several hydroxyl groups.
• the compound reactive with the isocyanate comprises or consists of a polyol.
• the polyol is selected from the group consisting of polyester polyols, polyether polyols, polycarbonate diols, polysiloxane diols, polyalkylene diols and mixtures thereof. More preferably, the polyol is a polyether polyol, a polyester polyol and/or a polycarbonate diol, such that the flexible blocks of the thermoplastic polyurethane are polyether blocks, polyester blocks and/or polycarbonate blocks, respectively. More preferably, the flexible blocks of the thermoplastic polyurethane are polyether blocks and/or polyester blocks (the polyol being a polyether polyol and/or a polyester polyol).
• polyester polyol mention may be made of polycaprolactone polyols and/or copolyesters based on one or more carboxylic acids chosen from adipic acid, succinic acid, pentanedioic acid and/or sebacic acid and one or more alcohols chosen from 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1, 6-hexanediol and/or polytetrahydrofuran.
• carboxylic acids chosen from adipic acid, succinic acid, pentanedioic acid and/or sebacic acid and one or more alcohols chosen from 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol,
• the copolyester can be based on adipic acid and a mixture of 1,2-ethanediol and 1,4-butanediol, or the copolyester can be based on adipic acid, succinic acid, pentanedioic acid, sebacic acid or mixtures thereof, and polytetrahydrofuran (tetramethylene glycol), or the copolyester may be a mixture of these copolyesters.
• polyether polyol polyether diols (ie aliphatic ⁇ , ⁇ -dihydroxylated polyoxyalkylene blocks) are preferably used.
• the polyether polyol is a polyetherdiol based on ethylene oxide, propylene oxide, and/or butylene oxide, a block copolymer based on ethylene oxide and propylene, a polyethylene glycol, a polypropylene glycol, a polybutylene glycol, a polytetrahydrofuran, a polybutane diol or a mixture thereof.
• the polyether polyol is preferably a polytetrahydrofuran (flexible blocks of thermoplastic polyurethane therefore being blocks of polytetrahydrofuran) and/or a polypropylene glycol (flexible blocks of thermoplastic polyurethane therefore being blocks of polypropylene glycol) and/or a polyethylene glycol ( flexible blocks of thermoplastic polyurethane therefore being blocks of polyethylene glycol), preferably a polytetrahydrofuran having a number-average molar mass of 500 to 15,000 g/mol, preferably of 1,000 to 3,000 g/mol.
• the polyether polyol can be a polyether diol which is the reaction product of ethylene oxide and propylene oxide; the molar ratio of ethylene oxide to propylene oxide is preferably 0.01 to 100, more preferably 0.1 to 9, more preferably 0.25 to 4, more preferably 0 .4 to 2.5, more preferably from 0.6 to 1.5 and it is more preferably 1.
• the polysiloxane diols which can be used in the invention preferably have a number-average molar mass of 500 to 15,000 g/mol, preferably of 1,000 to 3,000 g/mol.
• the number average molar mass can be determined by GPC, preferably according to standard ISO 16014-1:2012.
• the polysiloxane diol is a polysiloxane of formula (I): HO-[RO]nR-Si(R')2-[O-Si(R')2]mO-Si(R')2-R -[OR] P -OH (I) in which R is preferably a C2-C4 alkylene, R' is preferably a C1-C4 alkyl and each of n, m and p independently represents an integer preferably comprised between 0 and 50, m more preferably being from 1 to 50, even more preferably from 2 to 50.
• the polysiloxane has the following formula (II): in which Me is a methyl group, or the following formula (III):
• the polyalkylene diols which can be used in the invention are preferably based on butadiene.
• the polycarbonate diols which can be used in the invention are preferably aliphatic polycarbonate diols.
• the polycarbonate diol is preferably based on an alkanediol. Preferably, it is strictly bifunctional.
• the preferred polycarbonate diols according to the invention are those based on butanediol, pentanediol and/or hexanediol, in particular 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methylpentane -(1,5)-diol, or mixtures thereof, more preferably based on 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, or mixtures thereof.
• the polycarbonate diol can be a polycarbonate diol based on butanediol and hexanediol, or based on pentanediol and hexanediol, or based on hexanediol, or can be a mixture of two or more of these polycarbonate diols .
• the polycarbonate diol advantageously has a number-average molar mass of 500 to 4000 g/mol, preferably of 650 to 3500 g/mol, more preferably of 800 to 3000 g/mol.
• the number average molar mass can be determined by GPC, preferably according to standard ISO 16014-1:2012.
• One or more polyols can be used as the isocyanate-reactive compound.
• the flexible blocks of the TPU are blocks of polytetrahydrofuran, of polypropylene glycol and/or of polyethylene glycol.
• a chain extender is used for the preparation of the thermoplastic polyurethane, in addition to the isocyanate and the compound reactive with the isocyanate.
• the chain extender can be aliphatic, araliphatic, aromatic and/or cycloaliphatic.
• the chain extender preferably has two isocyanate-reactive groups (also called “functional groups"). A single chain extender or a mixture of two or more chain extenders can be used.
• the chain extender is preferably bifunctional.
• chain extenders are diamines and alkanediols with 2 to 10 carbon atoms.
• the chain extender can be chosen from the group consisting of 1,2-ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2,3-butanediol , 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanediol, 1,4-dimethanol cyclohexane, neopentylglycol, hydroquinone bis (beta-hydroxyethyl ) ether (HQEE), di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona- and/or deca-alkylene glycol, their respective oli
• the chain extender is selected from the group consisting of 1,2-ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5 pentanediol, 1,6-hexanediol, and mixtures of these, and more preferably, it is chosen from 1,3-propanediol, 1,4-butanediol and/or 1,6-hexanediol. Even more preferably, the chain extender is a mixture of 1,4-butanediol and 1,6-hexanediol, more preferably in a molar ratio of 6:1 to 10:1.
• a catalyst is used to synthesize the thermoplastic polyurethane.
• TPUs are for example commercially available from Covestro (Desmopan range) and from BASF (Elastollan range).
• the compatibilizing agents can be chosen from molecules or macromolecules containing silane or alkoxysilane groups.
• the molecules used comprise one or more silane functions as well as a function chosen from amines, hydroxyls, epoxides, carboxylic acids or maleic anhydrides.
• the following molecules can be used: (3-aminopropyl)triethoxysilane, triethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-aminopropyldimethylethoxysilane, 3-(2-aminoethylamino)propyldimethoxymethylsilane.
• This type of product is sold by suppliers such as Gelest, Shinetsu, Dow Corning or Merck. [Polysiloxanes]
• the compatibilizing agents can be chosen from polysiloxanes having the following structure:
• A can be chosen from methyl, ethyl, propyl, isopropyl or pentyl groups, advantageously A is a methyl group.
• Polysiloxanes are high molecular weight silicone oils (between 40 kg/mol and 40 kg/mol) which are commercially available as masterbatches in various matrices.
• Examples of commercial polysiloxanes are MB 50 from Dow Corning.
• the compatibilizing agents are very advantageously chosen from copolyamides, comprising in particular fatty acid dimer, impact modifiers, in particular functionalized maleic anhydride or epoxide, TPUs, and mixtures thereof.
• the content by weight, relative to the total weight of the composition, of the PEBA is greater than that of the TPU.
• compositions according to the invention do not comprise: Particles of crosslinked polyurethane (PU); and/or thermoplastic SBS or SEBS.
• PU crosslinked polyurethane
• SEBS thermoplastic SBS or SEBS.
• composition according to the invention is thermoplastic, that is to say fusible.
• the melting point of this composition can be between 100 and 220°C, in particular between 120 and 190°C, preferably between 125 and 170°C.
• the composition has a tan 5 at 23° C. of less than or equal to 0.15, preferably less than or equal to 0.12, in particular less than 0.10.
• the tan 5 (or loss factor) at 23°C corresponds to the ratio of the modulus of loss E on the modulus of elasticity E measured at a temperature of 23 C by dynamic mechanical analysis (DMA). It can be measured according to the ISO 6721 standard dating from 2019, the measurement being carried out at a deformation of 0.1% in tension, at a frequency of 1 Hz, and at a heating rate of 2°C/min.
• DMA dynamic mechanical analysis
• the tan 5 makes it possible to characterize the elasticity of the composition: the lower the tan 5, the greater the springback.
• the tan 5 at 23°C of the composition can be from 0.05 to 0.06, or from 0.06 to 0.07, or from 0.07 to 0.08, or from 0.08 to 0.09 , or from 0.09 to 0.10, or from 0.10 to 0.11, or from 0.11 to 0.15.
• the dynamic coefficient of friction on a wet aluminum substrate measured at a speed of 50mm/min and up to an elongation of 25mm according to the SATRA TM 144: 2011 procedure is generally greater than 0.35 preferably greater than 0.45 .
• the invention relates to a method for preparing a composition as defined above, comprising the following steps:
• the mixture preferably in an extruder, preferably in a co-kneader, o from 20 to 90% by weight, preferably from 40 to 70%, by weight, of at least one copolymer with polyamide blocks and with blocks polyethers, in the molten state and o from 10 to 80%, preferably from 30 to 60%, by weight, of at least one crosslinked rubber powder, in particular from used tires, o from 0 to 5% of additives , preferably from 0.1 to 4%, especially from 1 to 2%; o from 0 to 40% of compatibilizing agents, preferably from 5 to 20%, in particular from 10 to 15%.
• the mixing step of the process can in particular be carried out by applying high shear, heating or irradiation to allow good dispersing the rubber powder particles within the PEBA copolymer matrix and therefore obtaining a homogeneous mixture.
• the invention relates to an article consisting of, or comprising at least one element consisting of or comprising, a composition as described above, said article preferably being chosen from footwear components such as soles, shoes which can be chosen from city shoes, indoor sports shoes (volleyball, badminton, etc.), outdoor sports shoes (trail, hiking, football, skiing, etc.), water shoes (surfing, kayaking, etc.).
• footwear components such as soles, shoes which can be chosen from city shoes, indoor sports shoes (volleyball, badminton, etc.), outdoor sports shoes (trail, hiking, football, skiing, etc.), water shoes (surfing, kayaking, etc.).
• parts of ski poles racket handles (tennis, badminton, etc.) and golf clubs, goalkeeper gloves (football, baseball, etc.), treadmills, aquatic equipment such as as diving shoes, parts for masks and snorkels, parts for spectacle frames (sleeve, temples, nose pads), frames for ski masks, parts allowing vibration isolation in electronics and on machines , shells for external batteries, automotive parts (seals, tips), toys, watch straps, buttons on machines (remote control buttons, etc.), seals, components for transport belts.
• aquatic equipment such as as diving shoes, parts for masks and snorkels, parts for spectacle frames (sleeve, temples, nose pads), frames for ski masks, parts allowing vibration isolation in electronics and on machines , shells for external batteries, automotive parts (seals, tips), toys, watch straps, buttons on machines (remote control buttons, etc.), seals, components for transport belts.
• the invention relates to a process for recycling an article according to the invention comprising the following successive steps: a) recovery, after optional separation, of at least part of said article made of thermoplastic material comprising a composition according to the invention, b) grinding the thermoplastic material to obtain particles, c) melting the particles obtained in the previous step to obtain a molten mixture, d) optionally, adding other components to the molten mixture, and e) optionally, the formation of granules, filaments or powders from the molten mixture obtained at the end of step c) or d), and f) optionally, shaping of the granules, filaments or powders.
• certain articles such as sports shoes comprising a sole consisting of a composition according to the invention, do not require a step of separating the different elements in step a): they can be directly ground and melted to form a new article of recycled thermoplastic material, for example a new sole for a sports shoe.
• the invention relates to granules, filaments or powders capable of being obtained according to the claimed recycling process.
• the invention relates to an article consisting of or comprising at least one element prepared from granules, filaments or powders capable of being obtained according to the claimed recycling process.
• This article may for example be a sole for a shoe, in particular for sports.
• polyamide designates throughout the description a homopolyamide or a copolyamide, that is to say the condensation products of polyamide monomers, in particular of lactams, of alpha-omega aminocarboxyl acids and/or of diacids carboxylics and diamines.
• the term “monomer” in the present description of the polyamides should be taken in the sense of “repeating unit”.
• a repeating unit of the polyamide consists of the association of a dicarboxylic acid with a diamine is particular. It is considered that it is the combination of a diamine and a dicarboxylic acid, that is to say the diamine.diacid couple (in equimolar quantity), which corresponds to the monomer. This is explained by the fact that individually, the dicarboxylic acid or the diamine is only a structural unit, which is not sufficient on its own to polymerize.
• the polyamides according to the invention comprise at least two different monomers, called “co-monomers”, ie at least one monomer and at least one co-monomer (monomer different from the first monomer), they comprise a copolymer such as a copolyamide abbreviated COPA. Copolyamides therefore result from the polycondensation of several monomers forming polyamide units.
• polyamides The nomenclature used to define polyamides is described in standard ISO 1874-1:1992 "Plastics - Polyamide materials (PA) for molding and extrusion - Part 1: Designation", in particular on page 3 (tables 1 and 2) and is well known to those skilled in the art.
• PA denotes polyamide
• L denotes the number of carbon atoms of the alpha-omega aminocarboxylic acid or of the lactam.
• polyamide is obtained by the polycondensation of alpha-omega aminocarboxylic acid or lactam containing L carbon atoms.
• M designates the number of carbon atoms of the diamine
• N designates the number of carbon atoms of the dicarboxylic acid.
• alpha omega aminocarboxylic acid mention may be made of C6 to C18 alpha omega aminocarboxylic acids, and in particular aminocaproic, amino-7-heptanoic, amino-11-undecanoic and amino-12-dodecanoic acid.
• lactam By way of lactam, mention may be made of C6 to C18 lactams and in particular caprolactam, oenantholactam and lauryllactam.
• dicarboxylic acid mention may be made of linear or branched aliphatic, cycloaliphatic or aromatic C6 to C18 dicarboxylic acids and in particular 1,4-cyclohexyldicarboxylic acid, butanedioic, adipic, azelaic, suberic, sebacic, dodecanedicarboxylic acids, octadecanedicarboxylic and terephthalic and isophthalic acids, but also dimerized fatty acids.
• diamines mention may be made of linear or branched, cyclic, saturated or unsaturated, C2 to C18 aliphatic diamines and in particular tetramethylenediamine, hexamethylenediamine, 1,10-decamethylenediamine, dodecamethylenediamine, trimethylhexamethylenediamine, 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-cyclo-hexyl-methane (PACM), and isophoronediamine (IPDA), 2,6-bis- (aminomethyl)-norbornane (BAMN) and piperazine (Pip).
• AMF bis-(4-aminocyclohexyl)
• copolymer is understood to mean a polymer resulting from the copolymerization of at least two types of chemically different monomer, called comonomers. A copolymer is therefore formed from at least two different repeating units. It can also be formed from three or more repeating patterns. More specifically, the term “block copolymer” or “block copolymer” means copolymers in the aforementioned sense, in which at least two distinct monomer blocks are linked by a covalent bond. The length of the blocks can be variable. Preferably, the blocks are composed of 1 to 1000, preferably 1 to 100, and in particular
• junction block An intermediate non-repeating unit called a junction block.
• thermoplastic elastomer is understood to mean a polymer comprising flexible segments and rigid segments, for example in the form of a block copolymer, in which the rigid segments disappear when the temperature increases. Alternatively, they may be mixtures combining the presence of a flexible elastomeric phase, crosslinked or not, dispersed in a rigid thermoplastic continuous phase. The blends may in particular be blends of a thermoplastic polymer with an elastomer.
• melting temperature means the temperature at which a partially crystalline polymer changes to the viscous liquid state, as measured during the first heating (Tf1) by differential calorimetric analysis (DSC) according to standard NF EN ISO 11 357-3 using a heating rate of 20°C/min.
• thermoplastic polymer is understood to mean a polymer having the property of softening when it is sufficiently heated, and which, on cooling, becomes hard again.
• the physical quantities, making it possible in particular to characterize the mechanical properties of the compositions according to the invention, are as defined below:
• the dynamic coefficient of friction on the substrate is measured at a speed of 50mm/min and up to an elongation of 25mm according to the SATRA TM 144: 2011 procedure;
• PEBA copolymer comprising blocks of PA 11 with a number-average molar mass of 600 g/mol and flexible blocks of PTMG with a number-average molar mass of 1000 g/mol, with a hardness of 35 Shore D.
• PEBA copolymer comprising rigid blocks of PA 12 with a number-average molar mass of 600 g/mol and blocks of PTMG with a number-average molar mass of 2000 g/mol, with a Shore D hardness of 25.
• PEBA copolymer comprising rigid blocks of PA 11 with a number-average molar mass of 1000 g/mol and blocks of PTMG with a number-average molar mass of 1000 g/mol, with a hardness of 40 Shore D.
• Lotader® AX8900 is a random copolymer of ethylene, acrylic ester and glycicyl methacrylate commercially available from SK chemicals.
• TyreXol® CW 50 is a crosslinked rubber powder derived from used tires commercially available from TRS, with a specific surface area of 0.12 m 2 /g.
• the D50 diameter of this powder is about 130 ⁇ m and the D90 is about 270 ⁇ m.
• -TyreXol® MM30 is a crosslinked rubber powder derived from used tires commercially available from TRS, with a specific surface area of 0.05 m 2 /g.
• the D50 diameter of this powder is about 340 ⁇ m and the D90 is about 550 ⁇ m.
• compositions EC2 to EI4 above were manufactured using an 18 mm ZSK twin-screw extruder (Coperion). The barrel temperature was set at 180°C and the screw speed was 280 rpm with a throughput of 8 kg/h. Compositions EI5 to EI15 were produced using a PR46 co-kneader (Buss). The temperatures of the barrel and of the take-up screw are regulated at 175 C. The speed of the co-kneader is fixed at 250 rpm and the take-up screw at 20 rpm with a flow rate of 15 kg/h.
• Composition EC1 is a cross-linked synthetic rubber plate.
• compositions were then dried under reduced pressure at 80° C. in order to reach a moisture content of less than 0.04%.
• composition is fusible, i.e. transforms under the effect of heat into a fluid melt, it is classified (+) while when the composition is not fusible, it is classified (- ).
• compositions according to the invention are recyclable fusible) and have a high dynamic coefficient of friction on a wet aluminum substrate, which gives them good anti-slip properties.

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• 2021
  • 2021-12-23 FR FR2114456A patent/FR3131329B1/fr active Active
• 2022
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