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
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F12/02—Monomers containing only one unsaturated aliphatic radical
  • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
  • C08F12/06—Hydrocarbons
  • C08F12/08—Styrene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
  • C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
  • C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
  • C08F36/06—Butadiene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
  • C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
  • C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
  • C08F36/08—Isoprene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
  • C08L9/06—Copolymers with styrene
• • 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
  • C08L2203/00—Applications
  • C08L2203/12—Applications used for fibers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2203/00—Applications
  • C08L2203/16—Applications used for films
• • 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
  • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four 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
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
  • C08L2205/18—Spheres
• • 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
  • C08L2207/53—Core-shell polymer

Definitions

• the present invention relates to a polymer composition having advantageous properties of transparency and impact resistance, in particular for the manufacture of sports articles.
• Transparent compositions based on polyamides incorporating impact additives are known in the state of the art. Such compositions are described for example in documents US 2007/0249789, US 2009/0247699 and US 2014/0275392.
• WO 2007/144531 discloses ternary mixtures of polyamides and block copolymers having particularly advantageous properties of transparency, impact resistance, heat resistance and chemical resistance.
• compositions having improved low temperature properties including impact resistance and notch sensitivity properties; while also preserving the advantageous optical (transparency) and mechanical properties (flexural modulus) obtained with the products of document WO 2007/144531.
• the invention firstly relates to a composition
• a composition comprising: (A) an amorphous or quasi-amorphous copolymer with polyamide blocks and polyether blocks, the polyamide blocks comprising cycloaliphatic units;
• (D) a multi-layered polymer comprising at least one layer (D1) and one layer (D2).
• the composition comprises, by weight: from 15 to 50%, preferably from 20 to 40%, more preferably from 25 to 35%, and even more preferably from 27 to 32% of copolymer (A);
• polymer (D) from 1 to 25%, preferably from 2 to 20%, more preferably from 3 to 15%, and even more preferentially from 5 to 12% of polymer (D).
• the polymer (D) is in the form of core-shell particles, the layer (D1) being the core layer and the layer (D2) being a layer of bark of the particles, and preferably the layer outermost bark.
• the layer (D1) of the polymer (D) is a polymer layer which comprises at least 50% by weight of units derived from isoprene or butadiene; and or
• the layer (D2) of the polymer (D) is a (meth) acrylic polymer layer, preferably comprising at least 70% by weight of units derived from C1-C12 alkyl (meth) acrylates, and comprising in a further manner preferred at least 80% by weight of units derived from C1-C4 alkyl methacrylate and / or C1-C8 alkyl acrylate.
• the layer (D1) of the polymer (D) has a glass transition temperature of less than or equal to 0.degree.
• (D2) of the polymer (D) has a glass transition temperature greater than or equal to 60 ° C.
• the polyamide blocks of the copolymer (A) are formed predominantly by weight of an equimolar association of at least one cycloaliphatic diamine and at least one dicarboxylic acid, preferably a linear aliphatic dicarboxylic acid.
• the cycloaliphatic diamine is chosen from bis- (3-methyl-4-aminocyclohexyl) -methane (BMACM), para-aminodicyclohexyl methane (PACM), isophoronediamine (IPD), bis ( 4-aminocyclohexyl) -methane (BACM), 2,2-bis (3-methyl-4-aminocyclohexyl) propane (BMACP), 2,6-bis (aminomethyl) norbornane (BAMN) and combinations thereof and preferably is bis- (3-methyl-4-aminocyclohexyl) -methane.
• BMACM bis- (3-methyl-4-aminocyclohexyl) -methane
• PAMN para-aminodicyclohexyl methane
• IPD isophoronediamine
• BMACP para-aminocyclohexyl) -methane
• BMACP 2,2-bis (3-methyl-4
• the aliphatic dicarboxylic acid is chosen from aliphatic dicarboxylic acids having from 6 to 36 carbon atoms, preferably from 9 to 18 carbon atoms, in particular from 1, 10-decanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid and 1,18-octanedecanedicarboxylic acid.
• the polyamide blocks of the copolymer (A) are chosen from blocks B.6, B.9, B.10, B.12, B.14, B.16, B.18 and their mixtures or copolymers.
• the polyamide blocks of the copolymer (A) have a number-average molecular weight of 500 to 12000 g / mol, preferably of 2000 to 6000 g / mol.
• the number average molecular weight (or number average molar mass) is set by the chain limiter content. It can be calculated according to the relation:
• niimiter number of moles of excess diacid
• Miimiteur Molar mass of excess diacid
• the polyether blocks of the copolymer (A) comprise units derived from at least one polyalkylene ether polyol, in particular a polyalkylene ether diol, preferably chosen from polyethylene glycol (PEG) and polypropylene glycol (PPG). , polytrimethylene glycol (PO3G), polytetramethylene glycol (PTMG) and mixtures or copolymers thereof.
• a polyalkylene ether diol preferably chosen from polyethylene glycol (PEG) and polypropylene glycol (PPG).
• PEG polyethylene glycol
• PPG polypropylene glycol
• PO3G polytrimethylene glycol
• PTMG polytetramethylene glycol
• the polyether blocks of the copolymer (A) have a number-average molecular weight of 200 to 4000 g / mol, preferably of 300 to 1100 g / mol.
• the polymer or copolymer (B) is a copolymer comprising amide units, and preferably a copolymer with polyamide blocks and polyether blocks.
• the polyamide blocks of the copolymer (B) are chosen from the blocks PA 12, PA 11, PA 10.10, PA 10.12, PA 10.14, PA 6.10, PA 6.12, PA 6.14 and PA 6.18, the PA blocks. 12 being preferred.
• the polyether blocks of the copolymer (B) comprise units derived from at least one polyalkylene ether polyol, in particular a polyalkylene ether diol, preferably chosen from polyethylene glycol (PEG) and polypropylene glycol (PPG). , polytrimethylene glycol (PO3G), polytetramethylene glycol (PTMG) and mixtures or copolymers thereof.
• a polyalkylene ether diol preferably chosen from polyethylene glycol (PEG) and polypropylene glycol (PPG).
• PEG polyethylene glycol
• PPG polypropylene glycol
• PO3G polytrimethylene glycol
• PTMG polytetramethylene glycol
• the component (C) is an amorphous homopolyamide or copolyamide; and preferably is a B.14 homopolyamide.
• the composition comprises, in addition to the constituents (A) to (D), one or more additives, preferably chosen from antistatic agents, dyes, stabilizers, such as thermal stabilizers and stabilizers. UV, nucleating agents, plasticizers, impact improvers and reinforcing agents.
• additives preferably chosen from antistatic agents, dyes, stabilizers, such as thermal stabilizers and stabilizers. UV, nucleating agents, plasticizers, impact improvers and reinforcing agents.
• the sum of the constituents (A) to (D) represents at least 90% by weight, preferably at least 95% by weight, more preferably at least 98% by weight, and even more preferably at least 99% by weight. % by weight of the composition.
• the invention also relates to a method of manufacturing a composition as described above, comprising a step of mixing the constituents (A), (B), (C), and (D), preferably in the state melted, and an extrusion or injection step.
• the invention also relates to an article consisting of the composition described above, or comprising a part consisting of the composition described above.
• the article is chosen from a fiber, a fabric, a film, a sheet, a ring, a tube and an injected part.
• the article is a sports article, such as a sports shoe element, a sports implement such as ice skates, ski bindings, rackets, sports bats, boards, horseshoes , flippers, golf balls; or an article of hobby or DIY; or a road tool or equipment; or a protective article, such as a helmet visor, telescope, telescope arm; or a vehicle component, such as a headlamp, rearview mirror, tank, especially car, moped, motorcycle, scooter.
• a sports article such as a sports shoe element, a sports implement such as ice skates, ski bindings, rackets, sports bats, boards, horseshoes , flippers, golf balls; or an article of hobby or DIY; or a road tool or equipment; or a protective article, such as a helmet visor, telescope, telescope arm; or a vehicle component, such as a headlamp
• the present invention overcomes the disadvantages of the state of the art. More particularly, it provides polymer compositions having advantageous optical (transparency) and mechanical (flexural modulus) properties, with improved impact resistance and low-temperature notch sensitivity.
• a multi-layer polymer (D) to a blend of polymers or copolymers (A), (B) and (C).
• the polymer (D) improves the properties in particular of impact resistance at low temperature, while preserving the other advantageous properties, in particular of transparency or flexural modulus, conferred by the mixture (A), (B) and (C)
• Figure 1 illustrates the Charpy impact resistance of samples X0, X3, X6 and X10 defined in Example 1.
• the temperature in ° C is shown on the abscissa, and the resilience in kJ / m 2 is on the ordinate.
• FIG. 2 illustrates the transmittance T at 560 nm (in%, in the ordinate on the left) and the haze in English H (in%, in ordinate on the right) as a function of the polymer content (D) (in %, as abscissa) in the composition.
• composition of the invention comprises polymers or copolymers
• Component (A) is an amorphous or quasi-amorphous copolymer with polyamide blocks and polyether blocks, the polyamide blocks comprising cycloaliphatic units.
• it is amorphous.
• amorphous is meant a polymer having only a glass transition temperature (Tg) and no melting temperature (Tf).
• quadsi-amorphous is meant a very slightly crystalline polymer having a glass transition temperature (Tg) and a melting temperature (Tf) such as the enthalpy of crystallization during the cooling step at a rate of 20. ° K / min in Differential Scanning Calorimetry (DSC), measured according to ISO Standard 1,1357-3: 2013, is less than 30 J / g, preferably less than 20 J / g, more preferably less than 15 J / g.
• DSC Differential Scanning Calorimetry
• the glass transition temperature (Tg) measured by DSC at a heating rate of 20 ° K / min according to the standards ISO 1,1357-1: 2009 and ISO 1,1357-2: 2013 is preferably greater than 75 ° C. More preferably, component (A) has a glass transition temperature of at least 90 ° C.
• component (A) is transparent, i.e. it has a transmittance greater than 75% at 560 nm on a 2 mm thick plate.
• the polyamide blocks (PA) may consist mainly of a combination (preferably equimolar) of at least one diamine and at least one dicarboxylic acid, the diamine (s) being predominantly cycloaliphatic and the dicarboxylic diacid (s) being predominantly linear aliphatic , the amide units may optionally include, but in a minority manner, at least one other polyamide comonomer.
• the PA blocks consist entirely of a cycloaliphatic diamine and a dicarboxylic acid, preferably a linear dicarboxylic acid (without a minority comonomer).
• the cycloaliphatic diamine (s) can be advantageously chosen from bis (3-methyl-4-aminocyclohexyl) -methane (BMACM), para-aminodicyclohexyl methane (PACM), isophoronediamine (IPD) and bis (4-aminocyclohexyl).
• BMACM bis (3-methyl-4-aminocyclohexyl) -methane
• PAM para-aminodicyclohexyl methane
• BAMN 2,6-bis (amino methyl) norbornane
• a single cycloaliphatic diamine, in particular BMACM is used as diamine.
• At least one non-cycloaliphatic diamine may also be included in the composition of the monomers of the amide units, preferably at most 30 mol% relative to the total diamines.
• Non-cycloaliphatic diamines that may be mentioned include linear aliphatic diamines, such as 1,4-tetramethylene diamine, 1,6-hexamethylenediamine, 1,9-nonamethylenediamine and 1,10-decamethylenediamine.
• the at least one aliphatic dicarboxylic acid may be chosen from aliphatic dicarboxylic acids having from 6 to 36 carbon atoms, preferably from 9 to 18 carbon atoms, in particular 1,10-decanedicarboxylic acid (sebacic acid), 1,12-dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid and 1,18-octadecanalcoholic acid.
• At least one non-aliphatic dicarboxylic acid may be used in the composition of the monomers of the amide units, preferably at most 15 mol% relative to the total of the dicarboxylic acids.
• the non-aliphatic dicarboxylic acid is chosen from aromatic diacids, in particular isophthalic acid (I), terephthalic acid (T) and mixtures thereof.
• One or more monomers may enter in a minority manner in the preparation of the amide units. They may be chosen in particular from lactams and alpha-omega amino carboxylic acids.
• the lactam is, for example, selected from caprolactam, oenantholactam and lauryllactam.
• the alpha-omega-aminocarboxylic acid is, for example, selected from aminocaproic acid, 7-amino-heptanoic acid, 11-amino-1-undecanoic acid or 12-amino-dodecanoic acid.
• the constituent (A) has amide units whose carbon number per amide is on average at least equal to 9.
• the PA blocks are preferably chosen from PA blocks B.6, PA B.9, PA B.10, PA B.12, PA B.14, PA B.16, PA B.18 and mixtures thereof.
• PA XY X represents the number of carbon atoms derived from the diamine residues
• Y represents the number of carbon atoms derived from the diacid residues (conventionally), when it is a question of numbers.
• the letter B represents the residue from the BMACM diamine.
• the number-average molecular mass of the PA blocks is advantageously between 500 and 12000 g / mol, preferably between 2000 and 6000 g / mol.
• the polyether units of the polyether (PE) blocks are, for example, derived from at least one polyalkylene ether polyol, in particular a polyalkylene ether diol, preferably chosen from polyethylene glycol (PEG), polypropylene glycol (PPG) and polytrimethylene. glycol (PO3G), polytetramethylene glycol (PTMG) and mixtures or copolymers thereof.
• PEG polyethylene glycol
• PPG polypropylene glycol
• PO3G polytetramethylene glycol
• PTMG polytetramethylene glycol
• the PE blocks can comprise polyoxyalkylene sequences with Nh chain ends, such sequences being obtainable by cyanoacetylation of aliphatic polyoxyalkylene aliphatic alpha-omega dihydroxy sequences known as polyetherdiols. More particularly, it is possible to use the so-called Jeffamine® products (for example Jeffamine® D400, D2000, ED 2003, XTJ 542, Huntsman's commercial products, reference is made to documents JP 2004346274, JP 2004352794 and EP 148201 1. .
• the number-average molecular mass of the PE blocks is advantageously between 200 and 4000 g / mol, preferably between 300 and 1100 g / mol.
• the copolymer (A) may be prepared, for example, by the following process:
• the PA blocks are prepared by polycondensation
• the comonomer or comonomers selected from lactams and alpha-omega aminocarboxylic acids;
• the PA blocks obtained are reacted with PE blocks in the presence of a catalyst.
• the formation reaction of the PA block may in particular be carried out at a temperature of 180 to 300 ° C., preferably of 200 to 290 ° C.
• the pressure in the reactor is preferably between 5 and 30 bar, and is preferably maintained for about 2 to 3 hours. We can then reduce slowly the pressure of the reactor to atmospheric pressure, and then distilling the excess water, for example for an hour or two.
• the carboxylic acid-terminated PA block having been prepared, the PE block and a catalyst can then be added.
• the PE block can be added one or more times, as can the catalyst.
• the PE block is first added, the reaction of the OH ends of the PE block and the COOH ends of the PA block begins with the formation of ester bonds and the removal of water. As much water as possible is removed from the reaction medium by distillation, and then the catalyst is introduced to complete the bonding of PA blocks and PE blocks.
• This second step can be carried out with stirring, preferably under a vacuum of at least 15 mmHg (2000 Pa), at a temperature such that the reagents and copolymers obtained are in the molten state.
• this temperature can be between 100 and 400 ° C, and most often 200 and 300 ° C.
• the reaction is monitored by measuring the torque exerted by the molten polymer on the stirrer or by measuring the electrical power consumed by the stirrer. The end of the reaction is determined by the value of the target torque or power.
• chain limiter chosen from dicarboxylic acids
• said dicarboxylic acid is used as chain limiter, which is introduced in excess relative to the stoichiometry of the diamine or diamines.
• the catalyst used is a derivative of a metal selected from the group consisting of titanium, zirconium and hafnium or a strong acid such as phosphoric acid, hypophosphorous acid or boric acid.
• the polycondensation can in particular be carried out at a temperature of 240 to 280 ° C.
• the copolymer (A) may comprise hydrophilic PE blocks, preferably PEG, PPG or PO3G type PE blocks, which gives an additional advantage of antistatic and waterproof properties to the composition (ie allowing the passage water vapor, but not liquid water).
• hydrophilic PE blocks preferably PEG, PPG or PO3G type PE blocks, which gives an additional advantage of antistatic and waterproof properties to the composition (ie allowing the passage water vapor, but not liquid water).
• the copolymer (A) is a block copolymer B.12 and PTMG blocks.
• Component (B) is a semi-crystalline polymer or copolymer comprising amide units.
• melt-crystalline is meant a polymer which has a melting temperature (Tf) in DSC according to the standard ISO 1,1357-3 of 2013, and an enthalpy of crystallization during the cooling step at a speed of 20 ° K / min in DSC measured according to the ISO 1 1357-3 standard of 2013 greater than 30 J / g, preferably greater than 40 J / g.
• Tf melting temperature
• the constituent (B) may in particular be a polyamide or a copolyamide.
• the constituent (B) advantageously has a melting temperature greater than 100 ° C., preferably greater than 150 ° C., measured by DSC according to the standard ISO 1,1357-3: 2013
• Component (B) advantageously has a glass transition temperature of less than 65 ° C. measured by DSC at a heating rate of 20 ° K / min according to the standards ISO 1 1357-1: 2009 and ISO 1 1357-2: 2013.
• component B comprises amide units and ether units.
• the amide units are preferably aliphatic or predominantly aliphatic (by weight).
• component (B) is a PA block and PE block copolymer.
• the amide units may be formed predominantly (by weight) from a lactam or an alpha, omega-amino carboxylic acid, and / or from an equimolar combination of at least one diamine and at least one diacid the carboxylic acid, the diamine (s) being preferably predominantly (by weight) linear aliphatic, the amide units possibly comprising, but in a minority (by weight), at least one other polyamide comonomer.
• the constituent (B) can advantageously include amide units of linear aliphatic nature whose carbon number per amide is on average at least equal to 9.
• the constituent (B) may thus comprise linear aliphatic PA blocks, in particular chosen from the blocks PA 12, PA 11, PA 10.10, PA 10.12, PA 10.14, PA 6.10, PA 6.12, PA 6.14 and PA 6.18.
• the PE units may in particular be chosen from those indicated above with respect to the constituent (A), advantageously being of the same nature and / or of a number-average molecular mass (to within 50%, preferably to about 20% or to 10%).
• the amide units of component (B) represent at least 50% by weight of said constituent.
• the ether units of component (B) represent at least 15% by weight of said constituent.
• component (B) is a polyamide
• it may be chosen in particular from PA 12 and PA 1 1, or optionally from PA 10.10, PA 10.12, PA 10.14, PA 6.10, PA 6.12, PA 6.14 and the AP 6.18.
• component (B) is a copolyamide, preferably in block form
• the amide units are preferably chosen from PA 12 and PA 11, or optionally from PA 10.10, PA 10.12, PA 10.14, PA 6.10, PA 6.12, PA 6.14 and PA 6.18.
• the component (B) is a block copolymer PA 12 and PTMG blocks.
• Component (C) is a polymer or copolymer comprising amide units, which is different from component (A) and component (B).
• It may be in particular a homopolyamide or an amorphous copolyamide, and preferably an amorphous homopolyamide.
• It can be chosen in particular from aliphatic polyamides and cycloaliphatic polyamides.
• a mixture of several polyamides or copolyamides can be used for component (C).
• the constituent (C) (or, when the constituent (C) is a mixture of polymers, at least one of these), comprises at least one unit having the diamine formula of C.sub.1 -C.sub.11 -diacid.
• the C.sub.1 -C.sub.18 diacid diamine repeating unit is a unit obtained from the polycondensation of at least one linear or branched aliphatic diamine, or at least one cycloaliphatic diamine or a mixture of two or more thereof. ci and at least one aliphatic dicarboxylic acid or at least one cycloaliphatic dicarboxylic acid.
• the molar proportions of diamine and of dicarboxylic acid are preferably stoichiometric.
• the diamine and the dicarboxylic acid each comprise from 4 to 36 carbon atoms and advantageously from 6 to 18 carbon atoms.
• the aliphatic diamine used to obtain this repeating diamino-Cb-diacid repeat unit is as defined above for the diamine X.
• the cycloaliphatic diamine may be chosen for example from bis (3,5-dialkyl-4-aminocyclohexyl) -methane, bis (3,5-dialkyl-4-aminocyclohexyl) ethane, bis (3,5-dialkyl) -4 aminocyclohexyl) propane, bis (3,5-dialkyl-4-aminocyclohexyl) butane, bis (3-methyl-4-aminocyclohexyl) methane or 3'-dimethyl-4,4'-diamino -dicyclohexyl-methane commonly known as "BMACM” or "MACM” (and noted B below), p-bis (aminocyclohexyl) -methane commonly known as "PACM” (and noted hereinafter P), isopropylidènedi (cyclohexylamine ) commonly referred to as "PACP”, isophorone diamine (denoted IPD here
• the dicarboxylic acid may be chosen from linear or branched aliphatic dicarboxylic acids and cycloaliphatic dicarboxylic acids.
• dicarboxylic acid is aliphatic and linear, it is as defined above for the diacid Y.
• the dicarboxylic acid when it is cycloaliphatic, it may comprise the following carbon skeletons: norbornyl methane, cyclohexane, cyclohexylmethane, dicyclohexylmethane, dicyclohexylpropane, di (methylcyclohexyl) or di (methylcyclohexyl) propane.
• PA B.10, PA P.10, PA B.12, PA P.12, PA B.14, PA P.14, PA B.18 and PA P.18 By way of examples of preferred copolyamides, mention may be made of: PA 1 1 / B.10, PA 1 1 / P.10, PA 1 1 / B.12, PA 1 1 / P.12, PA 1 1 / B.14, PA 1 1 / P.14, PA 1 1 1 / B.18, PA 1 1 / P.18, PA 12 / B.10, PA 12 / P.10 , PA 12 / B.12, PA 12 / P.12, PA 12 / B.14, PA 12 / P.14, PA 12 / B.18, PA 12 / P.18, PA 10.10 / B.10, PA10.10 / P.10, PA 10.10 / B.12, PA 10.107P.12, PA 10.10 / B.14, PA
• the component (C) is a polyamide PA B.14.
• Component (D) is a multi-layered polymer comprising at least one layer (D1) and one layer (D2).
• the layers (D1) and (D2) are of different composition.
• Such a polymer can be formed sequentially by a multistage polymerization process, and preferably by a multistage emulsion polymerization process, resulting in the formation of at least one layer (D1) comprising a first polymer and the layer (D2) comprising a second polymer.
• the second polymer is formed by emulsion polymerization in the presence of the first emulsion polymer.
• the multilayer polymer according to the invention preferably comprises between 0 and 50% by weight of units comprising an aromatic group.
• the multilayered polymer is preferably in the form of essentially spherical polymer particles. These particles are also called "heart-bark".
• the first layer (D1) forms the core, the second layer (D2) or all subsequent layers form the respective bark or bark.
• the particles preferably have a weight average size of 20 nm to 500 nm, preferably 30 nm to 400 nm, more preferably 50 nm to 350 nm, still more preferably 75 nm to 300 nm, and most preferably 100 to 200 nm.
• the layer (D1) comprises a polymer having a glass transition temperature of less than or equal to 0 ° C and the layer (D2) comprises a polymer having a glass transition temperature greater than or equal to 60 ° C, the layer (D2 ) being disposed externally with respect to the layer (D1).
• the polymer of the layer (D1) has a glass transition temperature of less than or equal to -5 ° C, more preferably less than or equal to -15 ° C, preferably less than or equal to -25 ° C.
• the polymer of the layer (D2) has a glass transition temperature of 60 to 150 ° C.
• the polymer having a glass transition temperature of less than or equal to 0 ° C in the layer (D1) may be manufactured in particular in a first step of a multi-step process, forming the core of the multilayer polymer particles; the polymer having a glass transition temperature greater than or equal to 60 ° C can be manufactured in particular in a last step of a multi-step process, forming the outermost layer of the multilayer polymeric particles.
• One or more additional intermediate layers obtained by one or more intermediate steps may be present.
• the layer (D1) of the component (D) preferably comprises from 0% by weight to less than 50% by weight of units containing aromatic groups.
• the layer (D2) of the component (D) preferably comprises from 0% by weight to less than 50% by weight of units containing aromatic groups.
• the layer (D2) does not comprise aromatic group-containing units.
• the polymer of the layer (D1) having a glass transition temperature below 0 ° C it preferably comprises at least 50% by weight of units derived from isoprene or butadiene. It is preferred that this layer (D1) is the innermost layer (core or core) of the multilayer polymeric particles. It may be in particular homopolymers of isoprene or homopolymers of butadiene, of isoprene-butadiene copolymers, of isoprene copolymers with at most 98% by weight of a vinyl monomer and of butadiene copolymers. with not more than 98% by weight of a vinyl monomer.
• the vinyl monomer may be styrene, an alkylstyrene, acrylonitrile, an alkyl (meth) acrylate or butadiene or isoprene or mixtures thereof, the polymer of the layer (D1) preferably comprising less than 50% by weight. weight of monomers containing aromatic groups.
• the polymer of the layer (D1) can be crosslinked.
• Crosslinking monomers useful in the present invention include, but are not limited to, aromatic polyfunctional vinyl compounds such as divinylbenzene and divinyltoluene, polyhydric alcohols such as ethylene glycol dimethacrylate and 1,3-butanediol diacrylate, trimethacrylates, triacrylates, allyl carboxylates such as allyl acrylate and allyl methacrylate, and di- and tri-allylic compounds such as diallyl phthalate, diallyl sebacate and triallyltriazine.
• the core is a homopolymer of butadiene.
• the core is a butadiene-styrene copolymer.
• the glass transition temperature of the polymer of the layer (D1) comprising at least 50% by weight of polymer units derived from isoprene or butadiene is between -100 ° C and 10 ° C, so still more preferably between -80 ° C and 0 ° C and preferably between -70 ° C and -20 ° C.
• the polymer of the layer (D2) mention may be made of homopolymers and copolymers formed from monomers containing double bonds and / or vinyl monomers.
• the polymer of the layer (D2) is a (meth) acrylic polymer.
• the polymer of the layer (D2) comprises at least 70% by weight of monomers chosen from C1-C12 alkyl (meth) acrylates. Still more preferably, it comprises at least 80% by weight of C1 to C4 alkyl methacrylate monomers and / or C1 to C8 alkyl acrylate monomers.
• the acrylic or methacrylic monomers of the polymer of the layer (D2) are chosen from methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, methacrylate and methacrylate. ethyl, butyl methacrylate and mixtures thereof, in the wherein the polymer of the layer (D2) has a glass transition temperature of at least 60 ° C.
• the polymer of the layer (D2) may comprise units derived from functional monomers chosen from glycidyl (meth) acrylate, acrylic or methacrylic acid, amides derived from these acids, such as, for example, dimethylacrylamide, acrylate and the like. or 2-methoxyethyl methacrylate, 2-aminoethyl acrylates or methacrylates and mixtures thereof.
• it comprises at least 70% by weight of units derived from methyl methacrylate.
• the glass transition temperature of this polymer is between 60 ° C and 150 ° C.
• the glass transition temperature of the polymer is more preferably from 80 ° C to 150 ° C, preferably from 90 ° C to 150 ° C, and more preferably from 100 ° C to 150 ° C.
• the polymer of the layer (D2) is grafted onto the polymer of the layer (D1).
• the polymer of the (D2) layer is crosslinked.
• the multilayered polymer can be obtained by a multistage process, comprising at least two steps. Such a method is described for example in US 2009/0149600 or EP0722961.
• the polymer of the layer (D1) having a glass transition temperature below 0 ° C is manufactured in the first step of the multi-step process.
• the polymer of the layer (D2) having a glass transition temperature above 60 ° C is manufactured after the step of manufacturing the polymer of the layer (D1).
• the polymer of the layer (D2) having a glass transition temperature of greater than 60 ° C made during step (B) forms the outer layer of the multilayer polymeric particle. Additional intermediate steps may be present, leading to the formation of intermediate layers.
• the weight ratio of the polymer of the layer (D1) to the full multilayer polymer is preferably at least 60% by weight, preferably at least 70% by weight, more preferably from at least 75% by weight.
• the weight ratio of the polymer of the layer (D2) to the full multilayer polymer is preferably at least 5% by weight, preferably at least 6% by weight, more preferably from minus 7% by weight. Preferably, this ratio is at most 30% by weight.
• the ratio between the polymer of the layer (D1) and the complete multilayer polymer is between 5% by weight and 30% by weight.
• (meth) acrylic refers to any type of acrylic and methacrylic monomers.
• (meth) acrylic polymer indicates that the (meth) acrylic polymer essentially comprises polymers comprising (meth) acrylic monomers which constitute 50% by weight or more of the (meth) polymer acrylic.
• the multi-layered polymer is of the core-shell type based on methacrylates, butadiene and styrene (MBS copolymer).
• composition according to the invention may comprise one or more additives.
• antistatic additives and / or additives may for example be supplemented with antistatic additives and / or additives to increase the compatibility of the mixture with other polymers.
• additives may be chosen from dyes, stabilizers such as thermal stabilizers and UV stabilizers, nucleating agents, plasticizers, impact-improving agents and reinforcing agents, said additive (s) preferably having a refractive index close to that of the constituents (A), (B), (C), and (D).
• the composition preferably has a glass transition temperature above 75 ° C.
• the melting point of the composition is preferably greater than 100 ° C, more preferably greater than 150 ° C.
• the composition is transparent, that is to say that its transmittance at 560 nm on a 2 mm thick plate is greater than 75%.
• the constituents (A), (B), (C) and (D) can be mixed in the form of granules, this mixture then being injected at a temperature of between 230 and 330 ° C. on an injection press to obtain the desired objects and test pieces.
• the constituents (A), (B), (C), and (D) can also be melt blended, in particular in an extruder, at a temperature of between 230 and 330 ° C., so as to recover them. in the form of granules, which will subsequently be injected at a temperature between 230 and 330 ° C, on an injection molding machine to obtain the desired objects and test pieces.
• Some constituents may be mixed together, or with additives, before being mixed with the other constituents and / or additives.
• Each component (A), (B), (C), and (D) is preferably a single component. However, it is also possible in some cases to use two or more constituents of each category.
• the total content of additives in the composition is preferably less than or equal to 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2% or 1% by weight.
• the weight content of component (D) in the (total) composition may be in particular: from 1 to 2%, or from 2 to 3%, or from 3 to 4%, or from 4 to 5%, or from 5 to 6% %, or 6 to 7%, or 7 to 8%, or 8 to 9%, or 9 to 10%, or 10 to 12%, or 12 to 14%, or 14 to 16% , or 16 to 18%, or 18 to 20%, or 20 to 25%.
• the weight content of constituent (A) with respect to the sum (A) + (B) + (C) may be in particular: from 5 to 60%; preferably from 10 to 50%; more preferably from 20 to 40%; more preferably 25 to 38%, more preferably 30 to 35%; and more preferably about 32%.
• the weight content of constituent (B) with respect to the sum (A) + (B) + (C) may be in particular: from 10 to 70%; preferably from 20 to 65%; more preferably from 30 to 60%; more preferably from 35 to 55%, more preferably from 40 to 50%; and more preferably about 45%.
• the weight content of constituent (C) with respect to the sum (A) + (B) + (C) may be in particular: from 2 to 50%; preferably from 5 to 40%; more preferably from 10 to 35%; more preferably from 15 to 30%, more preferably from 20 to 25%; and more preferably about 23%.
• the present invention also relates to a shaped article, such as fiber, fabric, film, sheet, ring, tube, injected part, in particular transparent or translucent, comprising the composition as defined above, which can be produced in the form of dry mix or after compounding on an extruder.
• a shaped article such as fiber, fabric, film, sheet, ring, tube, injected part, in particular transparent or translucent, comprising the composition as defined above, which can be produced in the form of dry mix or after compounding on an extruder.
• composition according to the present invention is advantageous for the easy manufacture of articles, in particular articles or elements of sports articles, having in particular having both good transparency, good impact resistance and good endurance. mechanical, chemical, UV, thermal attack.
• sports shoes which may be in particular studded shoes such as soccer shoes, rugby shoes, football boots, running shoes, hiking shoes, ski or hockey shoes; sporting implements such as ice skates or other articles of winter sports and mountaineering, ski bindings, snowshoes, sports bats, boards, horseshoes, flippers, golf balls, golf, recreational vehicles, especially those for cold weather activities.
• protective items such as visors helmets, glasses, as well as glasses, shoulder protectors, elbow guards, back protectors, hand guards, knee guards, shin guards, including helmets, gloves, epaulets, elbow guards, knee pads.
• Non-limiting examples include car components, such as headlamps, mirrors, small parts of all-terrain vehicles, tanks, in particular, mopeds, motorcycles, scooters, subject to mechanical aggression. and chemical, PMMA hardware, cosmetic items subject to mechanical and chemical aggression, lipstick sticks, manometers, aesthetic protection elements such as gas cylinders.
• Block copolymer PA 12 (Mn 4000 g / mol) and PTMG blocks (Mn 1000 g / mol)
• multi-layer core-shell polymer based on methacrylates, butadiene and styrene MBS copolymer synthesized according to US 2009/149600 or EP 0722961.
• the multi-layered polymer D is synthesized according to Example 1 of US 2009/149600 as a first layer and according to Example 6 as a second layer, to obtain a multilayer MBS polymer.
• compositions according to the invention containing respectively 3%, 6% and 10% by weight of component (D), and of a comparative composition (X0) devoid of component (D), have been implemented by a compounding process:
• the samples were then processed by injection molding.
• the injection temperature was set at 270 ° C and the mold temperature at 40 ° C.

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• Polymers & Plastics (AREA)
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• 2016
  • 2016-05-17 FR FR1654352A patent/FR3051475B1/fr not_active Expired - Fee Related
• 2017
  • 2017-05-17 EP EP17731207.1A patent/EP3458519A1/fr not_active Withdrawn
  • 2017-05-17 JP JP2018560599A patent/JP2019520446A/ja active Pending
  • 2017-05-17 WO PCT/FR2017/051192 patent/WO2017198949A1/fr unknown
  • 2017-05-17 CN CN201780039524.3A patent/CN109415560A/zh active Pending
  • 2017-05-17 US US16/302,328 patent/US11142641B2/en active Active

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