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
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
  • C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic acids
• • 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
  • C08L2201/00—Properties
  • C08L2201/10—Transparent films; Clear coatings; Transparent materials

Definitions

• the present invention relates to the use of prepolymers in thermoplastic compositions comprising a matrix of at least one semi-crystalline transparent polyamide to improve the kinetics of crystallization and to reduce warpage over a prepolymer-free composition while retaining or improving the transparency properties (transmittance and Haze) as well as the mechanical properties of said composition without reducing its mechanical properties such as shock, module or Rossflex.
• the invention also relates to the compositions comprising the prepolymers as well as their use for extrusion or injection, in particular for the manufacture of articles obtained by extrusion, injection, in particular for the manufacture of sports shoes, especially footwear. football, ski boots or running, or compression molding.
• the invention also relates to a process for the preparation of said compositions and a method for manufacturing said sports articles as well as the articles obtained by said method.
• Thermoplastic compositions based on polyamide are raw materials that can be processed by extrusion, molding or injection, in particular by injection molding to manufacture plastic parts.
• thermoplastic compositions used must be characterized by a high transparency which then requires the use of a nucleating agent to help crystallize and avoid post-molding warpage.
• Nucleating agents such as talc are already known, in particular in patent applications US 2013/0150515 and EP2843726.
• nucleating agents such as talc have the disadvantage of diffusing light in the polyamides and thus adversely affect the transparency of the composition.
• the levels of nucleating agent to be used lead to dimensional instability in annealing (warping) due to the fact that the composition does not crystallize sufficiently during the injection process.
• the present invention overcomes the disadvantages of the prior art.
• the invention makes it possible to achieve faster crystallization kinetics and decreased warpage, in particular during annealing of the transparent polyamide semi-crystalline-prepolymer mixture at a temperature above the Tg of the transparent semi-crystalline polyamide. , while improving or maintaining excellent transparency properties (transmittance and Haze) as well as mechanical properties such as shock, module or Rossflex.
• the present invention relates to the use of at least one prepolymer in a composition comprising:
• composition being devoid of nucleating agent.
• the transparency of a material is defined according to two main criteria: the transmittance corresponding to the light transmission coefficient measured at a wavelength of 560 nm and for a plate thickness of 1 or 2 mm, in particular 2 mm according to the ISO standard 13468-2: 2006, and Haze determined according to D1003-97 (C).
• Haze or haze means a surface dullness, a haze, sail, "fog,” or fogging effect on the surface of the material. This effect is also known as Anglo-Saxon “fogging”. This effect can alter the transparency, the aesthetic appearance and the brightness of the surface of the object made of said material.
• semi-crystalline transparent polyamide within the meaning of the invention denotes transparent polyamides which have a melting point (Tf) and a melting enthalpy AH> 10 J / g, in particular> 12 J / g as well as a glass transition temperature (Tg) as determined by DSC according to the standard ISO 1,1357-1: 2009 and ISO 1,1357-2 and 3: 2013, at a heating rate of 20K / min.
• Tf melting point
• Tg glass transition temperature
• the semicrystalline transparent polyamide has a transmittance greater than or equal to 75% as measured at a wavelength of 560 nm and for a plate thickness of 2 mm according to the ISO 13468-2: 2006 standard.
• the semi-crystalline transparent polyamide has a Haze less than or equal to 30% as measured for a plate thickness of 2 mm according to the standard D1003-97 (C).
• the semicrystalline transparent polyamide has a transmittance greater than or equal to 75% as measured at a wavelength of 560 nm and for a plate thickness of 2 mm according to ISO 13468-2: 2006 and a Haze less than or equal to 30% as measured for a plate thickness of 2 mm according to the standard D1003-97 (C).
• the semicrystalline transparent polyamide has a transmittance greater than or equal to 85% as measured at a wavelength of 560 nm and for a plate thickness of 1 mm according to ISO 13468-2: 2006.
• the semi-crystalline transparent polyamide has a Haze less than or equal to 15% as measured for a plate thickness of 1 mm according to the standard D1003-97 (C).
• the semicrystalline transparent polyamide has a transmittance greater than or equal to 85% as measured at a wavelength of 560 nm and for a plate thickness of 1 mm according to ISO 13468-2: 2006 and a Haze less than or equal to 15% as measured for a plate thickness of 1 mm according to the standard D1003-97 (C).
• the semi-crystalline transparent polyamide has a number average molecular mass greater than 10,000 g / mol.
• composition defined above is devoid of photochromic dye.
• polyamide denotes a homopolyamide, a copolyamide or a mixture thereof provided that said homopolyamide, copolyamide or mixture thereof is transparent, in particular has a transmittance greater than or equal to 75% such as defined above and semi-crystalline.
• the homopolyamide is either an aliphatic repeating unit of formula A:
• A is selected from a unit obtained from at least one aminocarboxylic acid, a unit obtained from at least one branched aminocarboxylic acid and a unit obtained from at least one lactam, or of formula X.Y:
• XY being a repeating unit obtained from the polycondensation of at least one cycloaliphatic diamine or at least one linear aliphatic diamine or branched or at least one arylamine and at least one dicarboxylic acid comprising from 4 to 36 carbon atoms, preferably from 6 to 18 carbon atoms.
• the repeating unit A is obtained from an aminocarboxylic acid comprising from 9 to 12 carbon atoms. It can thus be chosen from 9-aminononanoic acid (denoted 9), 10-aminodecanoic acid (denoted 10), 11-aminoundecanoic acid (denoted 1 1) and 12-aminododecanoic acid (denoted 12). ).
• the repeating unit A is obtained from 11-aminoundecanoic acid (1 1).
• Motif A is also obtained from a branched or branched aminocarboxylic acid.
• the total number of carbon atoms which corresponds to the sum of the number of carbon atoms of the main chain and the number of atoms of the branch or branches, is from 12 to 36, advantageously from 15 to 30, and preferably, from 18 to 24.
• the main chain of the amino-carboxylic acid advantageously comprises between 6 and 18 carbon atoms and, preferably, between 10 and 12 carbon atoms.
• the main chain may be formed by an aminodecanoic acid, an aminoundecanoic acid or an aminododecanoic acid
• the branch (es) alkyl (s) of the amino-carboxylic acid and / or lactam (c) can (wind) be linear (s) and meet the formula CxH2x-1, with x being a number integer greater than or equal to 1. It (s) can (wind) also be branched (s).
• N-heptylamino-1-undecanoic acid which will be noted 18 because it comprises a total of 18 carbon atoms, of which 1 1 on the main chain and 7 on the branching n- heptyl.
• Other advantageous amino carboxylic acids are N-heptyl-amino-12-dodecanoic acid (denoted 19), N-dodecyl-amino-1 1 -undecanoic acid (denoted 23), N-dodecyl acid.
• amino-12-dodecanoic acid (noted 24), N-octadecylamino-1-undecanoic acid (noted 29) and N-octadecylamino-12-dodecanoic acid (noted 30).
• the repeat unit X.Y is a unit obtained from the polycondensation of at least one cycloaliphatic diamine or at least one linear or branched aliphatic diamine or at least one arylamine and at least one dicarboxylic acid.
• the molar proportions of cycloaliphatic diamine and dicarboxylic acid are preferably stoichiometric.
• the cycloaliphatic diamine may be chosen from bis (3,5-dialkyl-4-aminocyclohexyl) -methane, bis (3,5-dialkyl-4-aminocyclohexyl) ethane and bis (3,5-dialkyl-4-aminocyclohexyl) ) -propane, bis (3,5-dialkyl-4-aminocyclohexyl) butane, bis (3-methyl-4-aminocyclohexyl) -methane or 3,3'-dimethyl-4,4'-diamino dicyclohexyl methane commonly referred to as "BMACM” or "MACM” (and noted B hereinafter), p-bis (aminocyclohexyl) methane commonly known as "PACM” (and noted hereinafter P) or Dicykan®, isopropylidene di (cyclohexylamine) commonly referred to as "PACP”, is
• the cycloaliphatic diamine of the XY unit is chosen from 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane (B), p-bis (aminocyclohexyl) methane (P) and isophoronediamine (IPD). or their mixtures.
• the cycloaliphatic diamine of the XY unit is a bicycloaliphatic diamine, in particular chosen from 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane (B), p-bis (aminocyclohexyl) methane (P) or mixtures thereof.
• the arylamine may be chosen from metaxylene diamine (MXD) or paraxylene diamine or mixtures thereof.
• the dicarboxylic acid may be chosen from linear or branched aliphatic dicarboxylic acids, cycloaliphatic dicarboxylic acids and aromatic dicarboxylic acids.
• the dicarboxylic acid is aliphatic and linear, it can be chosen from succinic acid (4), pentanedioic acid (5), adipic acid (6), heptanedioic acid (7), acid octanedioic acid (8), azelaic acid (9), sebacic acid (10), undecanedioic acid (1 1), dodecanedioic acid (12), brassylic acid (13), tetradecanedioic acid (14), hexadecanedioic acid (16), octadecanedioic acid (18), octadecenedioic acid (18), eicosanedioic acid (20), docosanedioic acid (22) and fatty acid dimers containing 36 carbons.
• succinic acid (4) pentanedioic acid (5), adipic acid (6), heptanedioic acid (7), acid
• the fatty acid dimers mentioned above are dimerized fatty acids obtained by oligomerization or polymerization of unsaturated monobasic fatty acids with a long hydrocarbon chain (such as linoleic acid and oleic acid), as described in particular in the document EP 0 471 566.
• copolyamide may comprise more than two distinct repeating units and in particular three then answering the formula A XY / Z in which Z is a similar pattern but different from A or a similar pattern but different from XY
• the semi-crystalline transparent polyamide may also be a mixture of semi-crystalline polyamide and amorphous polyamide provided that it has a melting point, a melting enthalpy of AH> 10 J / g, in particular> 12 J / g, with a heating rate of 20K / min, as well as a glass transition temperature as determined by DSC according to the ISO 1 1357 standard.
• said semi-crystalline transparent mixture may also be a mixture of semi-crystalline polyamide and amorphous polyamide and has a transmittance greater than or equal to 75% as measured at a wavelength of 560 nm and for a plate thickness.
• semi-crystalline polyamide is generally understood to mean linear aliphatic polyamides whose crystallinity is manifested by the presence of spherulites of sufficiently large size for the material to have a transmittance of less than 75% at 560 nm over plate 2 mm thick (according to ISO 13468-2: 2006).
• aliphatic polyamides which are of formula A or X.Y as defined above, as well as the other polyamides provided that they are semi-crystalline.
• amorphous polyamides is intended to mean amorphous transparent polyamides having a melting enthalpy of not more than 3J / g, preferably not more than 1 J / g as determined during the second heating in DSC according to 1 1357-3: 2013 at a heating rate of 20K / min.
• the cycloaliphatic diamines are as defined above.
• a PEBA was mixed with said homopolyamide, copolyamide or mixture thereof or else with a semi-crystalline polyamide or with amorphous polyamide or with said mixture of semi-crystalline polyamide and amorphous polyamide.
• Polyamide sequences with dicarboxylic chain ends with polyoxyalkylene sequences with diamine chain ends obtained by cyanoethylation and hydrogenation of aliphatic dihydroxylated polyoxyalkylene aliphatic sequences called polyether diols.
• polyamide sequences with dicarboxylic chain ends with polyetherdiols the products obtained being, in this particular case, polyetheresteramides.
• the copolymers (C) are advantageously of this type.
• the polyamide sequences with dicarboxylic chain ends result, for example, from the condensation of alpha-omega-aminocarboxylic acids, lactams or dicarboxylic and diamine diacids in the presence of a dicarboxylic acid chain-limiting agent.
• the molar mass in number Mn of the polyamide sequences is between 300 and 15,000 and preferably between 600 and 5,000.
• Mn polyether sequences is between 100 and 6000 and preferably between 200 and 3000.
• Polymers with polyamide blocks and polyether blocks may also comprise randomly distributed units. These polymers can be prepared by the simultaneous reaction of the polyether and the precursors of the polyamide blocks.
• polyetherdiol, a lactam (or an alpha-omega amino acid) and a chain-limiting diacid can be reacted in the presence of a little water.
• a polymer having essentially polyether blocks, polyamide blocks of very variable length, but also the various reagents reacted randomly are obtained which are distributed statistically along the polymer chain.
• These polymers with polyamide blocks and polyether blocks whether they come from the copolycondensation of previously prepared polyamide and polyether blocks or from a one-step reaction, have, for example, Shore D durations which can be between 20 and 75 and advantageously between 30 and 75. and 70 and intrinsic viscosity between 0.8 and 2.5 measured in meta-cresol at 25 ° C for an initial concentration of 0.8 g / 100 ml.
• the MFI can be between 5 and 50 (235 ° C under a load of 1 kg)
• the polyetherdiol blocks are either used as such and copolycondensed with polyamide blocks having carboxylic ends, or they are aminated to be converted into polyether diamines and condensed with polyamide blocks having carboxylic ends. They can also be mixed with polyamide precursors and a chain limiter to make the polyamide block and polyether block polymers having statistically distributed patterns.
• an inorganic nucleating agent such as, for example, a metal oxide, metal particles, silica, alumina, clay or talc
• an organic nucleating agent such as an additional polyamide having a melting temperature (Tf2) greater than the melting point (Tfi) of the polyamide to be nucleated, in particular a melting temperature Th> Tf + 20 ° C, the PA 6.6 or polyphthalamides being preferred;
• the prepolymer is not a nucleating agent and is therefore excluded from nucleating agents, particularly as defined above.
• prepolymer refers to oligomers of polyamides necessarily of number average molecular weight less than that of the polyamides used in the matrix, in particular said prepolymer with a number-average molecular mass of from 1000 to 15000 g / mol, in in particular from 1000 to 10000 g / mol.
• the prepolymer may be chosen from oligomers of linear or branched aliphatic polyamides, oligomers of cycloaliphatic polyamides, oligomers of semi-aromatic polyamides, oligomers of aromatic polyamides, linear or branched aliphatic polyamides, cycloaliphatic and semi-aromatic polyamides. aromatics having the same definition as above.
• the prepolymer or oligomer is therefore derived from condensation:
• the prepolymer or oligomer can not therefore correspond to the condensation of a diamine with a lactam or an amino acid.
• the prepolymer may also be a copolyamide oligomer or a mixture of oligomers of polyamides and copolyamide.
• the prepolymer is monofunctional Nh, monofunctional CO2H or difunctional CO2H or NH2.
• the prepolymer is monofunctional, preferably NH 2 or CO2H.
• Obtaining NH 2 monofunctional prepolymers can be carried out by reacting a (linear or branched) alkyl or aryl monocarboxylic acid after condensation of a lactam or an amino acid or a diamine with a dicarboxylic acid.
• Obtaining diNH2 prepolymers can be carried out by reacting a diamine after condensation of a lactam or an amino acid or a diamine with a dicarboxylic acid.
• Obtaining monofunctional CO2H prepolymers can be carried out by reacting a (linear or branched) alkyl or aryl monocarboxylic acid after condensation of a lactam or an amino acid or a diamine with a dicarboxylic acid.
• Obtaining diCO2H prepolymers may be effected by reacting a dicarboxylic acid after condensation of a lactam or an amino acid or a diamine with a dicarboxylic acid.
• non-functional diCH3 prepolymers can be effected by reacting the amine endings of the prepolymer with a monocarboxylic acid alkyl and acid termini with an alkyl amine.
• the prepolymer is not in admixture with an additive such as alumina silicate.
• the prepolymer is added to said polyamide only in order to accelerate the crystallization and not to improve the overmolding when said polyamide is molded in particular with a thermoplastic polyurethane.
• the composition may also comprise at least one additive chosen from impact modifiers, core-shell modifiers, antistatic fillers, lubricants, dyes, pigments, brighteners, antioxidants, flame retardants and fibers, in particular aramid fibers, glass fibers, carbon fibers, advantageously glass fibers, fillers, in particular silica, graphite, expanded graphite, carbon black, glass beads, kaolin, magnesia, slags, wollastonite, nanofillers (carbon nanotubes) and stabilizers.
• additives chosen from impact modifiers, core-shell modifiers, antistatic fillers, lubricants, dyes, pigments, brighteners, antioxidants, flame retardants and fibers, in particular aramid fibers, glass fibers, carbon fibers, advantageously glass fibers, fillers, in particular silica, graphite, expanded graphite, carbon black, glass beads, kaolin, magnesia, slags, wollastonite, nanofillers (carbon nanotubes) and stabilize
• additives can not be photochromic dyes.
• composition after adding the additives must retain its transparency properties.
• the usual stabilizers used with polymers are phenols, phosphites, UV absorbers, stabilizers of HALS (Hindered Amine Light Stabilizer) type, metal iodides, etc. Examples include Irganox 1010, 245, 1098, Irgafos 168, Tinuvin 312, Iodide P201 from Ciba.
• impact modifier is understood to mean a polyolefin-based polymer having a flexural modulus of less than 100 MPa measured according to the ISO 178: 2010 standard and Tg of less than 0 ° C. (measured according to the standard 1,1357). 2 at the inflection point of the DSC thermogram), in particular a polyolefin, coupled or not with a Peba having a flexural modulus ⁇ 200 MPa.
• the impact modifier polyolefin may be functionalized or non-functionalized or be a mixture of at least one functionalized and / or at least one non-functionalized.
• the polyolefins carry a functional group chosen from carboxylic acid, carboxylic anhydride and epoxide functions, and is in particular chosen from a copolymer of ethylene and elastomeric propylene (EPR), an ethylene-propylene-diene copolymer with an elastomeric nature (EPDM) and an ethylene / alkyl (meth) acrylate copolymer, an ethylene-higher alkene copolymer, in particular an ethylene-octene copolymer, a ethylene-alkyl acrylate-maleic anhydride terpolymer.
• EPR ethylene and elastomeric propylene
• EPDM ethylene-propylene-diene copolymer with an elastomeric nature
• EPDM ethylene / alkyl (meth) acrylate copolymer
• an ethylene-higher alkene copolymer in particular an ethylene-octene copolymer, a
• the impact modifier is chosen from the following mixtures: F493 / Lotader®, in particular F493 / Lotader® 5500 or F493 / Lotader® 7500.
• core-shell modifier is also referred to as “core-shell copolymer”.
• the "core-shell type modifier” is in the form of fine particles having an elastomer core and at least one thermoplastic shell, the size of the particles is generally less than the ⁇ and advantageously between 150 and 500 nm.
• the "core-shell type modifier” has an acrylic or butadiene base, in contrast to the impact modifier which has a polyolefin base.
• a core By way of example of a core, mention may be made of homopolymers of isoprene or butadiene, copolymers of isoprene with at most 30 mol% of a vinyl monomer and copolymers of butadiene with at most 30 mol% of a vinyl monomer.
• the vinyl monomer may be styrene, alkylstyrene, acrylonitrile or an alkyl (meth) acrylate.
• Another core family is homopolymers of an alkyl (meth) acrylate and copolymers of an alkyl (meth) acrylate with at most 30 mol% of a vinyl monomer.
• the alkyl (meth) acrylate is advantageously butyl acrylate.
• the vinyl monomer may be styrene, alkylstyrene, acrylonitrile, butadiene or isoprene.
• the core of the copolymer (A) may be crosslinked in whole or in part.
• these monomers can be selected from poly (meth) acrylic esters of polyols such as butylene di (meth) acrylate and trimethylol propane trimethacrylate.
• Other difunctional monomers are, for example, divinylbenzene, trivinylbenzene, vinyl acrylate and vinyl methacrylate.
• the core may also be cross-linked by grafting or as a comonomer during the polymerization, unsaturated functional monomers such as unsaturated carboxylic acid anhydrides, unsaturated carboxylic acids and unsaturated epoxides. Mention may be made, for example, of maleic anhydride, (meth) acrylic acid and glycidyl methacrylate.
• the bark or barks are homopolymers of styrene, alkylstyrene or methyl methacrylate or copolymers comprising at least 70 mol% of one of these monomers and at least one comonomer selected from the other monomers above , vinyl acetate and acrylonitrile.
• the bark may be functionalized by introducing, by grafting or as comonomer during the polymerization, unsaturated functional monomers such as unsaturated carboxylic acid anhydrides, unsaturated carboxylic acids and unsaturated epoxides. Mention may be made, for example, of maleic anhydride, (meth) acrylic acid and glycidyl methacrylate.
• core- bark copolymers (A) with two barks, one made of polystyrene and the other outside PMMA are also core - bark copolymers (A) with two barks, one made of polystyrene and the other outside PMMA. Examples of copolymer (A) as well as their method of preparation are described in the following patents: US 4,180,494, US 3,808,180, US 4,096,202, US 4,260,693, US 3,287,443, US 3,657,391, US 4,299,928, US 3,985,704.
• the "core-shell type modifier is therefore different from the polyolefin of the impact modifier and in particular that the impact modifier reacts with the polyamide matrix while the core-shell does not react with it because the heart of the latter is likely to react only with the bark of this one.
• the Applicant has therefore surprisingly found that the use of a prepolymer in a semi-crystalline transparent polyamide composition makes it possible to improve the kinetics of crystallization and to reduce the warpage of said composition while preserving or improving its transparency properties.
• the prepolymer therefore accelerates the crystallization of the semi-crystalline transparent polyamide without disturbing the transparency, which allows said composition to have a better dimensional stability with a prepolymer than without a prepolymer or with a nucleating agent, at a rate which makes it possible to preserve the transparency> 75% in 2 mm. Indeed, in the absence of prepolymer without nucleating agent the composition continues to crystallize during a heat treatment and in particular during decoration which induces a warping.
• the composition In the presence of the only nucleating agent the crystallization is accelerated but the nucleating agent has a negative impact on the optical properties of the semi-crystalline transparent polyamide.
• the nucleating agent When the nucleating agent is introduced at a rate which makes it possible to retain the transparency> 75% in 2 mm, the composition then continues to crystallize during a heat treatment and in particular during the decoration which induces a warping.
• composition of the invention comprising the semi-crystalline transparent polyamide and the prepolymer has the same transparency as said semi-crystalline transparent polyamide, and whether said composition comprises an additive or not.
• composition with which said prepolymer is used comprises: said matrix consisting of said at least one semicrystalline transparent polyamide in a proportion of 60 to 99.95% by weight, in particular 55 to 99.95%;
• the proportion by weight of polyamide and that of prepolymer being respectively from 60 to 99.9% and from 40 to 0.1%, relative to the sum transparent polyamide semicrystalline -prepolymer;
• said additive in proportion by weight of 0 to 20%
• the sum of the semi-crystalline transparent polyamide, the prepolymer and optionally the additive being equal to 100%.
• said matrix defined above consists of at least one semicrystalline transparent homopolyamide, in particular said semi-crystalline transparent homopolyamide has a transmittance greater than or equal to 75% as measured at a wavelength of 560 nm and for a plate thickness of 2 mm according to ISO 13468-2: 2006.
• said semi-crystalline transparent homopolyamide is of formula XY, in particular chosen from P.10, B.10, P.12, B.12, MXD.6, MXD.10, PXD.10, MXD.12 and PXD.12.
• said matrix defined above consists of at least one semi-crystalline transparent copolyamide, in particular said semi-crystalline transparent copolyamide has a transmittance greater than or equal to 75% as measured at a wavelength of 560 nm and for a plate thickness of 2 mm according to ISO 13468-2: 2006.
• said semi-crystalline transparent copolyamide is of formula A / X.Y.
• the molar proportion of repeating unit A in said transparent semi-crystalline copolyamide of formula A XY is from 91% to less than 100%. Therefore, the mole content of repeat unit XY is less than or equal to 9%. Indeed, it is observed that from 91% mole content of repeating unit A in copolyamide A XY, the repeating units A and XY being as defined above, the rigidity, transparency and fatigue criteria. are reached regardless of the processing conditions. In particular, the implementation by molding is quite satisfactory: no warpage ("warpage" in English) of the molded mass is observable. For a mole content of less than 91%, it is observed on the contrary that the copolyamide no longer responds to the fatigue test "Ross Flex".
• the unit A in a proportion of from 95% to less than 100% by mole and the X.Y unit in a proportion of from more than 0 to less than 5% by mole.
• the repeating unit A in said semicrystalline transparent copolyamide of formula A XY is a PA1 1 or PA12, the XY unit being a homopolyamide comprising a cycloaliphatic diamine, in particular the XY unit is chosen from Bl (I corresponding to isophthalic acid), B.10, P.10, B.12, P.12.
• said semi-crystalline transparent copolyamide is of formula A / X.Y / Z.W in which A and X.Y are as defined above and Z.W are as defined for X.Y with the proviso that Z.W is different from X.Y.
• the molar proportion of repeating unit A in said transparent semi-crystalline copolyamide of formula A / X.Y / Z.W is from 91% to less than 100%. Therefore, the mole content of repeat unit X.Y and Z.W is less than or equal to 9% with the proviso that the mole content of each of the repeat units X.Y or Z.W is greater than 0.
• the repeating unit A in said semicrystalline transparent copolyamide of formula A / XY / ZW is a PA1 1 or PA12, the XY unit being a homopolyamide comprising a cycloaliphatic diamine, in particular the XY unit is chosen from Bl (I corresponding to isophthalic acid), B.10, P.10, B.12, P.12 and the ZW unit being a homopolyamide comprising a cycloaliphatic diamine, in particular the XY unit is chosen from Bl (I corresponding to isophthalic acid ), B.10, P.10, B.12, P.12 provided that XY is different from ZW
• the transparent semi-crystalline polyamide and the prepolymer must be compatible with each other, that is to say that they do not exhibit macroscopic phase separation when they are mixed.
• the prepolymer is chosen from long-chain polyamides and is compatible with the polyamide of the matrix, in particular the polyamide of the matrix is chosen from long-chain polyamides, in particular aliphatic polyamides, semi-aromatic or cycloaliphatic.
• said prepolymer corresponds to a polyamide, in particular an aliphatic one, in particular chosen from PA6, PA1 1, PA12, PA1 1/6 and PA6 / 12 or a mixture of these.
• a single prepolymer is used in the composition.
• Said prepolymer used in a composition of the invention may have a number-average molecular weight of from 1000 to 15000 g / mol, especially from 1000 to 13000 g / mol, especially from 1000 to 10000 g / mol, especially from 1000 to 9000 g / mol.
• g / mole in particular from 1000 to 8000 g / mole, in particular from 1000 to 7000 g / mole, in particular from 1000 to 6000 g / mole, in particular from 1000 to 5000 g / mole, in particular from 2000 to 5000 g / mole, in particular from 2000 to 4000 g / mol, in particular from 2000 to 3000 g / mol.
• the proportion by weight of prepolymer is from 0.1 to 20%, especially from 1 to 20% by weight, preferably from 1 to 15% by weight, more preferably from 1 to 10% by weight, still more preferably from 1 to 20% by weight. at 5% by weight relative to the total weight of the composition.
• the proportion by weight of prepolymer is from 1 to 30%, especially from 3 to 25% relative to the weight of semi-crystalline transparent polyamide prepolymer.
• the prepolymer may comprise a carbon number per nitrogen atom different from that of the transparent semi-crystalline polyamide, or the same to that of the semi-crystalline transparent polyamide or close to that of the transparent semi-crystalline polyamide.
• the semi-crystalline transparent polyamide and the prepolymer can therefore both be long-chained or both short-chain or the semi-crystalline transparent polyamide is long-chain and the short-chain prepolymer, or semi-transparent transparent polyamide.
• crystalline is short-chain and the prepolymer is long-chain.
• the prepolymer used consists of PA1 1.
• the prepolymer is used in a composition in which the additives are chosen from core-shell modifiers, stabilizers, dyes, plasticizers, flame retardants, fibers and fillers.
• the prepolymer is used in a composition in which the additives are chosen from stabilizers, dyes, plasticizers, flame retardants, fibers and fillers.
• the prepolymer is chosen from a prepolymer, diChb, diNh, monoNh, mono acid, diacid and amino acid.
• the prepolymer is monoNH 2 or monoacid or diacid.
• the present invention relates to a composition
• a composition comprising:
• composition being devoid of nucleating agent and impact modifier.
• said composition comprises a semicrystalline transparent copolyamide having a transmittance greater than or equal to 75% as measured at a wavelength of 560 nm and for a plate thickness of 2 mm according to the ISO 13468-2: 2006 standard. .
• said composition comprises a semi-crystalline transparent copolyamide of formula A XY, in particular having a transmittance greater than or equal to 75% as measured at a wavelength of 560 nm and for a plate thickness of 2 mm according to the standard ISO 13468-2: 2006, in which the molar proportion of unit A in A / XY copolyamide is greater than or equal to 91%.
• the molar proportion of unit A in said transparent semi-crystalline copolyamide A / X.Y of said composition is from 95% to less than 100%.
• the unit A of said semicrystalline transparent copolyamide of formula A / XY of said composition is a PA1 1 or PA12, the XY unit being a homopolyamide comprising a cycloaliphatic diamine, in particular the XY unit is chosen from P.10, B .10, P.12, B.12, MXD.6, MXD.10, PXD.10, MXD.12 and PXD.12.
• said composition of the invention comprises a semi-crystalline transparent copolyamide of formula A / XY / ZW, in particular having a transmittance greater than or equal to 75% as measured at a wavelength of 560 nm and for a plate thickness of 2 mm according to ISO 13468-2: 2006, in which A and XY are as defined above and ZW are as defined for XY with the proviso that ZW is different from XY
• the molar proportion of repeating unit A in said semicrystalline transparent copolyamide of formula A XY / ZW of said composition of the invention ranges from 91% to less than 100%. Therefore, the mole content of repeating unit XY and ZW is less than or equal to 9% provided that the mole content of each of the XY or ZW repeating units is greater than 0.
• the repeating unit A in said semicrystalline transparent copolyamide of formula A / XY / ZW of said composition of the invention is a PA1 1 or PA12, the XY unit being a homopolyamide comprising a cycloaliphatic diamine, in particular the XY unit is selected from Bl (I corresponding to isophthalic acid), B.10, P.10, B.12, P.12 and the ZW unit being a homopolyamide comprising a cycloaliphatic diamine, in particular the XY unit is chosen from Bl ( I corresponding to isophthalic acid), B.10, P.10, B.12, P.12 provided that XY is different from ZW
• said composition comprises a prepolymer compatible with said polyamide.
• said composition comprises a prepolymer which corresponds to a polyamide, in particular aliphatic, especially chosen from PA6, PA1 1, PA12, PA 1 1/6 and PA6 / 12 or a mixture thereof.
• the prepolymer present in the composition of the invention has a number-average molecular mass of from 1000 to 15000 g / mol, in particular from 1000 to 13000 g / mol, in particular from 1000 to 10000 g / mol, preferably from 1000 to 5000 g / mole.
• the prepolymer present in said composition of the invention is in proportion by weight of prepolymer of 0.1 to 20%, especially 1 to 20%, especially 3 to 15%, relative to the total of the composition.
• the proportion by weight of prepolymer present in said composition of the invention is from 1 to 30%, especially from 3 to 25% relative to the weight of prepolymer-polyamide.
• the prepolymer present in said composition of the invention consists of PA1 1.
• the additives of said composition are chosen from core-shell modifiers, stabilizers, dyes, plasticizers, flame retardants, fibers and fillers.
• composition of the invention comprises:
• At least one additive chosen from core-shell modifiers, stabilizers, colorants, plasticizers, flame retardants, fibers and fillers;
• composition being devoid of nucleating agent and impact modifier.
• the semi-crystalline transparent copolyamide of this latter composition has a transmittance greater than or equal to 75% and is 1 1 / B.I.
• the invention relates to the use of a composition as defined above, for the manufacture of articles obtained by extrusion, injection or molding.
• Articles obtained by extrusion may be films or sheets for thermoforming thereafter, or tubes or pipes for dispensing fluids, including gasoline, compressed air or refrigerant.
• the articles obtained by injection are for example sports articles, especially sports shoes and especially ski boots, football or running shoes.
• the present invention relates to a process for the preparation of articles as defined above, comprising a step of extruding, injecting or molding the composition defined above.
• the present invention relates to articles as obtained by the method defined above.
• the present invention relates to a process for preparing a composition
• a process for preparing a composition comprising contacting a prepolymer with at least one semi-crystalline transparent polyamide and optionally at least one additive,
• polyamide being present in a proportion of 60 to 99.95% by weight, in particular 55 to 99.95% by weight;
• said prepolymer being present in a proportion of from 0.05% to 20% by weight, the proportion by weight of polyamide and that of prepolymer being respectively 60 to 99.9% and 40 to 0.1%, relative to the polyamide-prepolymer sum;
• said additive being in proportion by weight of 0 to 20%
• the sum of the polyamide, the prepolymer and optionally the additive being equal to 100%
• composition being devoid of nucleating agent
• composition having improved crystallization kinetics and decreased warpage while maintaining or improving its transparency properties as well as its mechanical properties compared to the same prepolymer-free composition.
• the polyamide composition used in the invention can be prepared by compounding the transparent polyamide of the matrix, the prepolymer and optionally the additive, optionally a release agent and any other components.
• the composition is usually recovered in the form of pellets or granules.
• the polyamide composition used in the invention can also be prepared by dry blend. Description of figures
• BMVO (1 1 / B.I having a proportion in PA1 1 greater than 91% and less than 100 mol% and a proportion B.l less than 9% and greater than 0%, produced by the applicant).
• Figure 2 shows DMA curves (dynamic mechanical analysis) of longitudinal and transverse expansion of BMVO samples injected and then heated at 90 ° C in the DMA apparatus.
• the dilation and / or the warping are measured by the longitudinal and transverse movements of the part. It is considered that the warpage of the part will be proportional to the difference in longitudinal and transverse displacements after cooling of the part.
• BMVO (1 1 / B.I having a proportion in PA1 1 greater than 91% and less than 100 mol% and a proportion B.l less than 9% and greater than 0%, produced by the applicant).
• Bars 80x10x4 mm 3 were made by injection molding. The following process parameters were used:
• Plates of 100x100x1 mm 3 were made by injection molding. The following process parameters were used:
• prepolymer PA1 1 mono NH2 defined above.
• Optical microscopy analyzes show that the addition of 5 or 10% PA1 1 monoNH2 oligomer leads at a more heterogeneous and coarser crystallinity at the core but leads to a lesser skin effect with an amorphous zone from about 70 ⁇ to less than 10 ⁇ (see Table III).
• Table IV shows the Te values measured according to ISO 1,1357-3: 2013 and the half crystallization time at 164 ° C (measured according to ISO 1,1357-7: 2013)
• Table IV shows that the addition of a prepolymer to a polyamide in a proportion by weight of 1 to 10% very significantly accelerates the kinetics of crystallization.
• Examples 1 and 2 were reproduced using a monofunctional acid or difunctional diacid prepolymer.
• the difunctional PA1 1 prepolymer NH 2 and CO 2 H although decreasing the warping of the BMVO injection or annealing, however, does not remove it completely, especially annealing, unlike monofunctional prepolymer mono NH2.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Proteomics, Peptides & Aminoacids (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Polyamides (AREA)
• Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
• Injection Moulding Of Plastics Or The Like (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=54545326

Family Applications (1)

Country Status (7)

Families Citing this family (4)

Family Cites Families (26)

• 2015
  • 2015-09-22 FR FR1558911A patent/FR3041354B1/fr active Active
• 2016
  • 2016-09-20 CN CN201680055203.8A patent/CN108137922B/zh active Active
  • 2016-09-20 JP JP2018515067A patent/JP6918788B2/ja active Active
  • 2016-09-20 WO PCT/FR2016/052373 patent/WO2017051105A1/fr active Application Filing
  • 2016-09-20 KR KR1020187010128A patent/KR102552794B1/ko active IP Right Grant
  • 2016-09-20 US US15/759,009 patent/US11299626B2/en active Active
  • 2016-09-20 EP EP16781512.5A patent/EP3353243A1/fr active Pending
• 2021
  • 2021-03-30 JP JP2021056652A patent/JP2021107553A/ja active Pending

Also Published As

Similar Documents

Legal Events