EP3325537A1 - Halbkristalline polyamidzusammensetzung mit einer hohen glasübergangstemperatur für ein thermoplastisches material, herstellungsverfahren dafür und verwendungen davon - Google Patents

Halbkristalline polyamidzusammensetzung mit einer hohen glasübergangstemperatur für ein thermoplastisches material, herstellungsverfahren dafür und verwendungen davon

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Publication number
EP3325537A1
EP3325537A1 EP17745845.2A EP17745845A EP3325537A1 EP 3325537 A1 EP3325537 A1 EP 3325537A1 EP 17745845 A EP17745845 A EP 17745845A EP 3325537 A1 EP3325537 A1 EP 3325537A1
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EP
European Patent Office
Prior art keywords
composition
reactive
polymer
mol
polyamide polymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP17745845.2A
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English (en)
French (fr)
Inventor
Mathieu Capelot
Gilles Hochstetter
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Arkema France SA
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Arkema France SA
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Publication date
Application filed by Arkema France SA filed Critical Arkema France SA
Publication of EP3325537A1 publication Critical patent/EP3325537A1/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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

Definitions

  • the invention relates to a novel composition of semi-crystalline polyamide (SE) of high glass transition temperature, based on bis (aminomethyl) cyclohexane (BAC), for thermoplastic material.
  • SE semi-crystalline polyamide
  • BAC bis (aminomethyl) cyclohexane
  • thermoplastic material It also relates to the method of manufacturing said thermoplastic material and the uses of said composition for the manufacture of mechanical parts or structure based on said material for pieces of material and the resulting part and for applications in the fields.
  • CN10421 1953 discloses a polyamide composition
  • a polyamide composition comprising from 30 to 99.9% by weight of a polyamide resin comprising from 60 to 95% by moles of 10T, from 5 to 40% by moles of 5T, 5 'corresponding to the 2-methyl-1,5-pentamethylenediamine, from 0 to 70% by weight of a reinforcing filler and from 0.1 to 50% by weight of an additive.
  • the polyamide resin has a melting temperature above 260 ° C.
  • EP 550 314 describes, among its examples, (non-reactive) copolyamide compositions in search of melting temperatures above 250 ° C and limited Tg's with most of the examples cited having a Tg too low ( ⁇ 80 ° C) or too high Tf (> 300 ° C).
  • EP 1 988 13 discloses a molding composition based on a 10T / 6T copolyamide with:
  • polyamides having a high melting point and greater than 270 ° C. are used.
  • the examples mentioned and Figure 1 teach us that the melting temperature of these compositions is at least about 280 ° C.
  • WO 201 1/003973 describes compositions comprising from 50 to 95 mol% of a linear aliphatic diamine-based unit containing from 9 to 12 carbon atoms and terephthalic acid and from 5 to 50% of a unit-forming unit. terephthalic acid to a mixture of 2,2,4 and 2,4,4 trimethylhexanediamine.
  • US 201 1306718 discloses a method of pultrusion of low Tg reactive aliphatic polyamides associated with chain extenders of polymeric structure bearing several (and much greater than 2) functions of anhydrides or epoxides. This document does not describe any non-polymeric extender.
  • WO 2014/064375 describes in particular a PA MXDT / 10T which has an excellent compromise between the various features described above.
  • MXD meta-xylenediamine monomer
  • thermoplastic material of the invention has as interest compared to amorphous polyamides, significantly improved mechanical performance, especially in hot, such as creep or fatigue resistance.
  • having a melting point above 200 ° C has the advantage in the automobile to be compatible with cataphoresis treatments, which does not allow an amorphous PA type structure.
  • a Tg greater than or equal to 90 ° C is required to ensure good mechanical properties of the thermoplastic material over the entire operating temperature range. for example up to 90 ° C for wind turbines, up to 100 ° C for cars and up to 120 ° C for aeronautics.
  • a melting point which is too high, in particular greater than 290 ° C. is, however, detrimental since it requires the use of the thermoplastic material at higher temperatures with the constraints of molding material to be used (and associated heating) and overconsumption of energy with in addition to the risks of thermal degradation by heating at temperatures higher than the melting temperature of said polyamide, with consequent assignment of the properties of the final thermoplastic matrix and the resulting material.
  • the crystallinity of said polymer must be as high as possible but with a not too high melting temperature Tf (Tf ⁇ 290 ° C. and more particularly ⁇ 280 ° C.) to optimize the mechanical performance and the crystallization rate and / or the temperature of the polymer. highest crystallization possible, this to reduce the molding time before ejection of the molded part with a selective choice of the composition of said semi-crystalline polyamide.
  • the object of the present invention is the implementation of new specific compositions of thermoplastic material, in particular based on semicrystalline polyamide, having a good compromise between high mechanical performance (mechanical strength), particularly when hot, easy to implement.
  • the solution of the invention in the case of reactive compositions, allows using compositions based on semi-crystalline reactive polyamide prepolymers, both a reaction kinetics and a fast crystallization kinetics with a cycle time. shorter.
  • the polyamide polymer matrix while having a high Tg and a limited Tf as defined, with an easy implementation of said thermoplastic material, must also have a high crystallization rate, characterized firstly by a difference between the melting temperature. and Tf-Tc crystallization not exceeding 40 ° C, preferably not exceeding 30 ° C. Therefore, the object of the invention is to develop a polyamide composition meeting the needs already defined above:
  • the present invention relates to a composition for a thermoplastic material comprising:
  • thermoplastic matrix based on at least one semicrystalline polyamide polymer, 0 to 50% of additives and / or other polymers
  • said semi-crystalline polyamide polymer being:
  • a) a reactive composition comprising or consisting of at least one precursor reactive polyamide prepolymer of said semicrystalline polyamide polymer,
  • composition b) a non-reactive composition of at least one polyamide polymer, said composition being that of said thermoplastic matrix defined above, and said reactive polyamide prepolymer of the composition a) and said polyamide polymer of the composition b) comprising or consisting of at least one BACT / XT copolyamide in which:
  • BACT is an amide unit unit present at a molar level ranging from 20 to 70%, preferably from 25 to 60%, more preferably from 35 to 55%, where BAC is selected from 1,3-bis (aminomethyl) cyclohexyl. (1, 3 BAC), 1,4-bis (aminomethyl) cyclohexyl (1,4BAC) and a mixture thereof, and T is terephthalic acid, - XT is an amide unit present at a molar level ranging from 30 to 80%, preferably from 40 to 75%, more preferably from 45 to 65%, where X is a linear aliphatic diamine of C 9 to C 18, preferably C 9, C 10, C 1 and C 12, and where T is terephthalic acid, preferentially C10, C1 and C12.
  • terephthalic acid in the BACT and / or XT units, independently of one another, up to 30 mol%, preferably 20 mol%, in particular up to 10 mol%, based on the total amount of dicarboxylic acids, terephthalic acid may be replaced by other aromatic, aliphatic or cycloaliphatic dicarboxylic acids containing 6 to 36 carbon atoms, in particular 6 to 14 carbon atoms, and
  • the BACT and / or XT units independently of one another, up to 30 mol%, preferably 20 mol%, in particular up to 10 mol%, of the BAC; and / or according to the case of X, relative to the total amount of the diamines, may be replaced by other diamines comprising from 4 to 36 carbon atoms, in particular from 6 to 12 carbon atoms, and
  • not more than 30 mol%, preferably not more than 20 mol%, preferably not more than 10 mol%, based on the total amount of the monomers, may be formed by lactams or acids aminocarboxylic, and
  • the sum of the monomers which replace terephthalic acid, BAC and X does not exceed a concentration of 30 mol%, preferably 20 mol%, preferably 10 mol%, relative to the total amount of monomers used in the copolyamide, and
  • BACT and XT units are always present in said polyamide polymer.
  • Said semi-crystalline polyamide polymer is thus the semi-crystalline polyamide polymer which is the base of the thermoplastic matrix, said thermoplastic matrix being able to be obtained from the reactive composition a) which corresponds to:
  • the semicrystalline polyamide polymer is already present in the non-reactive composition b).
  • the present invention relates to a composition for a thermoplastic material comprising:
  • thermoplastic matrix based on at least one semi-crystalline polyamide polymer, 0 to 50% of additives and / or other polymers
  • thermoplastic matrix being: a) a reactive composition comprising or consisting of at least one precursor reactive polyamide prepolymer of said semicrystalline polyamide polymer,
  • composition b) a non-reactive composition of at least one polyamide polymer, said composition being that of said thermoplastic matrix defined above, and said reactive polyamide prepolymer of the composition a) and said polyamide polymer of the composition b) comprising or consisting of at least one BACT / XT copolyamide in which:
  • BACT is an amide unit unit present at a molar level ranging from 20 to 70%, preferably from 25 to 60%, more preferably from 35 to 55%, where BAC is chosen from 1,3-bis (aminomethyl). cyclohexyl (1, 3 BAC), 1,4-bis (aminomethyl) cyclohexyl (1,4BAC) and a mixture thereof, and T is terephthalic acid,
  • XT is an amide unit present in a molar level ranging from 30 to 80%, preferably from 40 to 75%, more preferably from 45 to 65%, where X is a linear aliphatic diamine of C 9 to C 18, preferably C 9, C 10, C 1 and C 12, and where T is terephthalic acid, preferentially C10, C1 and C12.
  • terephthalic acid in the BACT and / or XT units, independently of one another, up to 30 mol%, preferably 20 mol%, in particular up to 10 mol%, based on the total amount of dicarboxylic acids, terephthalic acid may be replaced by other aromatic, aliphatic or cycloaliphatic dicarboxylic acids containing 6 to 36 carbon atoms, in particular 6 to 14 carbon atoms, and
  • the BACT and / or XT units independently of one another, up to 30 mol%, preferably 20 mol%, in particular up to 10 mol%, of the BAC and / or according to the case of X, relative to the total amount of the diamines, may be replaced by other diamines comprising from 4 to 36 carbon atoms, in particular from 6 to 12 carbon atoms, and
  • not more than 30 mol%, preferably not more than 10 mol%, based on the total amount of the monomers, may be formed by lactams or aminocarboxylic acids, and
  • the sum of the monomers which replace terephthalic acid, BAC and X does not exceed a concentration of 30 mol%, preferably 10 mol%, based on the total amount of the monomers used in the copolyamide, and provided that BACT and XT units are always present in said polyamide polymer.
  • said reactive polyamide prepolymer of the composition a) and said polyamide polymer of the composition b) comprising or consisting of at least one BACT / XT copolyamide means that the reactive polyamide prepolymer of the composition a) or said polyamide polymer of the composition b) consist exclusively of amide unit units BACT and XT in proportions respectively defined above, or the reactive polyamide prepolymer of the composition a) or said polyamide polymer of the composition b) comprise amide BACT units and XT in respective proportions defined above but also other units amide units.
  • the proportion of units units amide the proportion of BACT / XT BACT and XT in the reactive polyamide prepolymer of the composition a) or said polyamide polymer of the composition b) is greater than 50%, especially greater than 60%, in particular greater than 70%, preferably greater than 80%, especially greater than 90%.
  • the present invention therefore relates to a composition for a thermoplastic material comprising:
  • thermoplastic matrix based on at least one semi-crystalline polyamide polymer, 0 to 50% of additives and / or other polymers
  • said semi-crystalline polyamide polymer comprising or consisting of at least one BACT / XT copolyamide in which:
  • BACT is an amide unit unit present at a molar level ranging from 20 to 70%, preferably from 25 to 60%, more preferably from 35 to 55%, where BAC is selected from 1,3-bis (aminomethyl) cyclohexyl. (1, 3 BAC), 1,4-bis (aminomethyl) cyclohexyl (1,4BAC) and a mixture thereof, and T is terephthalic acid, - XT is an amide unit present at a molar level ranging from 30 to 80%, preferably from 40 to 75%, more preferably from 45 to 65%, where X is a linear aliphatic diamine of C 9 to C 18, preferably C 9, C 10, C 1 and C 12, and where T is terephthalic acid, preferentially C10, C1 and C12.
  • terephthalic acid in the BACT and / or XT units, independently of one another, up to 30 mol%, preferably 20 mol%, in particular up to 10 mol%, based on the total amount of dicarboxylic acids, terephthalic acid can be replaced by other aromatic, aliphatic or cycloaliphatic carboxylic acid diacids comprising 6 to 36 carbon atoms, in particular 6 to 14 carbon atoms, and
  • the BACT and / or XT units independently of one another, up to 30 mol%, preferably 20 mol%, in particular up to 10 mol%, of the BAC and / or according to the case of X, relative to the total amount of the diamines, may be replaced by other diamines comprising from 4 to 36 carbon atoms, in particular from 6 to 12 carbon atoms, and
  • not more than 30 mol%, preferably not more than 10 mol%, based on the total amount of the monomers, may be formed by lactams or aminocarboxylic acids, and
  • the sum of the monomers which replace terephthalic acid, BAC and X does not exceed a concentration of 30 mol%, preferably 10 mol%, based on the total amount of the monomers used in the copolyamide, and
  • BACT and XT units are always present in said polyamide polymer.
  • composition according to the invention may comprise short reinforcing fibers or short fibrous reinforcement).
  • the so-called short fibers are of length between 200 and 400 ⁇ .
  • These short reinforcing fibers may be chosen from:
  • the mineral fibers these having melting temperatures Tf that are higher than and higher than the melting temperature Tf of said semi-crystalline polyamide of the invention and greater than the temperature of polymerization and / or processing.
  • polymeric or polymer fibers having a melting temperature Tf or, in the absence of Tf, a glass transition temperature Tg ', greater than the polymerization temperature or greater than the melting temperature Tf of said semi-crystalline polyamide constituting said matrix of the material thermoplastic and superior to the temperature of implementation,
  • Suitable mineral fibers for the invention include carbon fibers, which include carbon nanotube or carbon nanotube (CNT) fibers, carbon nanofibers or graphenes; silica fibers such as glass fibers, especially of type E, R or S2; boron fibers; ceramic fibers, in particular silicon carbide fibers, boron carbide fibers, boron carbonitride fibers, silicon nitride fibers, boron nitride fibers, basalt fibers; fibers or filaments based on metals and / or their alloys; fibers of metal oxides, especially alumina (Al 2 O 3); metallized fibers such as metallized glass fibers and metallized carbon fibers or mixtures of the aforementioned fibers.
  • CNT carbon nanotube or carbon nanotube
  • Silica fibers such as glass fibers, especially of type E, R or S2
  • boron fibers ceramic fibers, in particular silicon carbide fibers, boron carbide fibers, boron carbonitrid
  • these fibers can be chosen as follows:
  • the mineral fibers may be chosen from: carbon fibers, fibers of carbon nanotubes, glass fibers, in particular of type E, R or S2, boron fibers, ceramic fibers, in particular silicon carbide fibers, carbide fibers of boron, boron carbonitride fibers, silicon nitride fibers, boron nitride fibers, basalt fibers, metal-based fibers or filaments and / or their alloys, metal oxide-based fibers such as AI203, fibers metallized materials such as metallized glass fibers and metallized carbon fibers or mixtures of the aforementioned fibers, and
  • polymer or polymer fibers under the abovementioned condition, are chosen from:
  • thermosetting polymer fibers and more particularly chosen from: unsaturated polyesters, epoxy resins, vinyl esters, phenolic resins, polyurethanes, cyanoacrylates and polyimides, such as bis-maleimide resins, aminoplasts resulting from the reaction an amine such as melamine with an aldehyde such as glyoxal or formaldehyde, thermoplastic polymer fibers and more particularly chosen from: polyethylene terephthalate (PET), polybutylene terephthalate (PBT),
  • aramid fibers such as Kevlar®
  • aromatic polyamides such as those corresponding to one of the formulas: PPD.T, MPD.I, PAA and PPA, with PPD and MPD respectively being p- and m-phenylene diamine, PAA being polyarylamides and PPA being polyphthalamides,
  • polyamide block copolymer fibers such as polyamide / polyether, polyarylether ketone fibers (PAEK) such as polyetheretherketone (PEEK), polyetherketoneketone (PEKK), polyetherketoneetherketoneketone (PEKEKK).
  • PAEK polyarylether ketone fibers
  • PEEK polyetheretherketone
  • PEKK polyetherketoneketone
  • PEKEKK polyetherketoneetherketoneketone
  • the preferred short reinforcing fibers are short fibers chosen from: carbon fibers, including metallized fibers, glass fibers, including metallized type E, R, S2, aramid fibers (such as Kevlar®) or aromatic polyamides, polyarylether ketone fibers (PAEK), such as polyetheretherketone (PEEK), polyetherketoneketone (PEKK) fibers, polyetherketoneetherketoneketone (PEKEKK) fibers or their mixtures.
  • carbon fibers including metallized fibers, glass fibers, including metallized type E, R, S2, aramid fibers (such as Kevlar®) or aromatic polyamides, polyarylether ketone fibers (PAEK), such as polyetheretherketone (PEEK), polyetherketoneketone (PEKK) fibers, polyetherketoneetherketoneketone (PEKEKK) fibers or their mixtures.
  • PEEK polyetheretherketone
  • PEKK polyetherketoneketone
  • PEKEKK
  • natural fibers are selected from flax, castor, wood, sisal, kenaf, coconut, hemp and jute fibers.
  • the reinforcing fibers present in the composition according to the invention are chosen from glass fibers, carbon fibers, from linseed fibers and their mixtures, and more preferentially flax fibers and carbon fibers, and more preferably still carbon fibers.
  • the composition according to a preferred variant of the invention more particularly comprises specific additives such as thermal stabilizers, in particular these stabilizers are antioxidants against thermo-oxidation and / or photo-oxidation of the thermoplastic matrix polymer and are organic or inorganic stabilizers.
  • thermal stabilizers in particular these stabilizers are antioxidants against thermo-oxidation and / or photo-oxidation of the thermoplastic matrix polymer and are organic or inorganic stabilizers.
  • organic stabilizer or more generally a “combination of organic stabilizers” denotes a primary antioxidant of phenol type, a secondary phosphite-type antioxidant and possibly even other stabilizers such as HALS, which means Hindered Amine Light Stabilize or hindered amine light stabilizer (for example Tinuvin® 770 from Ciba), an anti-UV (for example Tinuvin® 312 from Ciba), a phenolic or phosphorus-based stabilizer. It is also possible to use amine-type antioxidants such as Naugard® 445 from Crompton or polyfunctional stabilizers such as Nylostab® S-EED from Clariant.
  • the organic stabilizer present can be chosen, without this list being restrictive, among:
  • phenolic antioxidants for example Irganox® 245, Irganox® 1010, Irganox® 1098 from Ciba, Irganox® MD1024 from Ciba, Lowinox® 44B25 from Great Lakes the ADK® Stab AO-80 from the company Adeka Palmarole.
  • phosphorus stabilizers such as phosphites, for example Irgafos® 168 from Ciba,
  • a UV absorber such as Tinuvin® 312 from Ciba
  • an amine-type stabilizer such as Naugard® 445 from Crompton, or else a hindered amine type such as Tinuvin® 770 from Ciba,
  • mineral stabilizer refers to a copper stabilizer.
  • mineral stabilizers By way of example of such mineral stabilizers, mention may be made of copper halides and acetates. Incidentally, one may consider other metals such as silver, but these are known to be less effective. These copper-based compounds are typically associated with alkali metal halides, particularly potassium.
  • These mineral stabilizers are more particularly used, when the structures must have an improved thermal resistance in the long term in hot air, especially for temperatures greater than or equal to 100-120 ° C, since they tend to prevent breaks in the polymer chains. .
  • copper-based stabilizer is intended to mean a compound comprising at least one copper atom, in particular in ionic form, ionizable, for example in the form of a complex.
  • the copper stabilizer may be selected from cuprous chloride, cupric chloride, cuprous bromide, cupric bromide, cuprous iodide, cupric iodide, cuprous acetate and cupric acetate.
  • halides acetates other metals such as silver in combination with the copper stabilizer.
  • These copper-based compounds are typically associated with alkali metal halides.
  • a well-known example is the mixture of Cul and Kl, where the ratio Cul: KI is typically between 1: 5 to 1:15.
  • An example of such a stabilizer is Polyadd P201 from Ciba.
  • copper stabilizers Further details on copper stabilizers can be found in US Patent 2,705,227. More recently, copper-based stabilizers have appeared such as complexed brass such as Bruggolen H3336, H3337, H3373 from Bruggemann.
  • the copper-based stabilizer is chosen from copper halides, copper acetate, copper halides or copper acetate mixed with at least one alkali metal halide, and mixtures thereof, preferably mixtures of copper iodide and potassium iodide (Cul / KI).
  • the additive may also be a shock modifier, advantageously constituted by a polymer having a flexural modulus of less than 100 MPa measured according to the ISO 178 standard and Tg of less than 0 ° C. (measured according to the standard 1 1357-2: 2013 at level of the inflection point of the DSC thermogram), in particular a polyolefin, coupled or not with a Peba having a flexural modulus ⁇ 200 MPa.
  • a shock modifier advantageously constituted by a polymer having a flexural modulus of less than 100 MPa measured according to the ISO 178 standard and Tg of less than 0 ° C. (measured according to the standard 1 1357-2: 2013 at level of 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 additives may also be fillers which may be in particular any filler known to those skilled in the field of thermoplastic materials. It may especially be heat-conducting and / or electrically conductive fillers, such as metal powder, powdery carbon black, carbon fibrils, carbon nanotubes (CNTs), carbide silicon, boron carbonitride, boron nitride or silicon.
  • CNTs carbon nanotubes
  • any reinforcing fibers, long, short or continuous, are excluded from the additives and in particular the term "inorganic filler" excludes long, short or continuous reinforcing fibers.
  • the additives may also be flame retardants, such as a metal salt selected from a metal salt of phosphinic acid, a metal salt of diphosphinic acid, a polymer containing at least one metal salt of phosphinic acid, a polymer containing at least one metal salt of diphosphinic acid.
  • a metal salt selected from a metal salt of phosphinic acid, a metal salt of diphosphinic acid, a polymer containing at least one metal salt of phosphinic acid, a polymer containing at least one metal salt of diphosphinic acid.
  • the additive is chosen from an antioxidant, a heat stabilizer, a UV absorber, a light stabilizer, a shock modifier, a lubricant, an inorganic filler, a flame retardant, a nucleating agent and a colorant. .
  • thermoplastic polymer denotes any thermoplastic polymer and in particular a polyamide polymer, especially an aliphatic, cycloaliphatic or aromatic polyamide, and which may be microcrystalline or amorphous.
  • nonreactive composition means that the composition is based on polyamide polymer whose molecular weight is no longer likely to change during its implementation and therefore corresponding to the final polyamide polymer of the thermoplastic matrix.
  • polyamides according to composition b) are non-reactive, either by the low level of reactive (residual) functions present, in particular with a level of said functions ⁇ 120 meq / kg, or by the presence of the same type of terminal functions at the end of the reaction. chain and therefore not reactive with each other, either by modifying and blocking said reactive functions by a monofunctional reactive component, for example for the amine functions by modification reaction with a monoacid or a monoisocyanate and for carboxyl functions by reaction with a monoamine.
  • a monofunctional reactive component for example for the amine functions by modification reaction with a monoacid or a monoisocyanate and for carboxyl functions by reaction with a monoamine.
  • the number-average molecular weight (Mn) of said final polyamide polymer of the thermoplastic matrix of said material is preferably in a range from 8000 to 40000 g / mol, preferably from 10000 to 30000 g / mol as determined by calculation. from the terminal function level determined by solution potentiometric titration and the functionality of said prepolymers or by NMR.
  • Mn values can correspond to inherent viscosities greater than or equal to 0.8, as determined according to ISO 307: 2007 but changing the solvent (use of m-cresol in place of sulfuric acid and the temperature being 20 ° C ).
  • reactive composition means that the molecular weight of said reactive composition will change during the implementation by reaction of prepolymers reactive with each other by condensation or with a chain extender by polyaddition and without elimination of under volatile products to lead to the final polyamide polymer of the thermoplastic matrix.
  • 1,3-BAC (or 1,3 bis (aminomethyl) cyclohexane, CAS No. 2579-20-6) is a cycloaliphatic diamine monomer obtained in particular by hydrogenation of metaxylene diamine (MXDA).
  • MXDA metaxylene diamine
  • 1,3-BAC exists as two cis and trans isomers, CAS No. 2579-20-6 corresponding to a mixture of isomers.
  • 1,4-BAC (or 1,4 bis (aminomethyl) cyclohexane, CAS No. 2549-07-9) is a cycloaliphatic diamine monomer obtained in particular by hydrogenation of para-xylene diamine (PXDA).
  • 1,4-BAC exists as two isomers, cis and trans, CAS No. 2549-07-9 corresponding to a mixture of isomers.
  • the 1,3-BAC or the 1,4-BAC used in the BACT unit is a mixture of cis and trans isomers in a proportion of 0/100 to 100/0, in particular 75/25 to 25/75.
  • the proportion of cis isomer in the 1.3 BAC is greater than 60%, preferably greater than 70%, in particular greater than 80%, especially greater than 90%.
  • the proportion of trans isomer in 1,4-BAC is greater than 60%, preferably greater than 70%, in particular greater than 80%, especially greater than 90%.
  • BAC and / or X may be replaced, independently of one another, up to 30 mol% by other diamines defined above, in particular by a linear or branched aliphatic diamine, a cycloaliphatic diamine or a arylaromatic diamine such as meta-xylene diamine (MXDA).
  • MXDA meta-xylene diamine
  • the linear or branched aliphatic diamine is chosen from 1,4-butanediamine, 1,5-pentanediamine, 2-methyl-1,5-pentanediamine (MPMD), 1,6 hexanediamine, 1,8-octanediamine (OMDA), 1,9-nonanediamine (NMDA), 2-methyl-1,8-octanediamine (MODA), 2,2,4-trimethylhexamethylenediamine (TMHMD), 2, 4,4-trimethylhexamethylenediamine (TMHMD), 5-methyl-1,9-nonanediamine, 1,1,1-undecanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 1,14-tetradecanediamine, 1,16-hexadecanediamine and 1,18-octadecanediamine.
  • MPMD 2-methyl-1,5-pentanediamine
  • OMDA 1,8-octanedia
  • the cycloaliphatic diamine may be chosen from isophoronediamine, norbornanedimethylamine, 4,4'-diaminodicyclohexylmethane (PACM), 2,2- (4,4'-diamino-dicyclohexyl) propane (PACP), and 3,3 4,4'-diaminodicyclohexylethane (MACM).
  • PAM 4,4'-diaminodicyclohexylmethane
  • PEP 2,2- (4,4'-diamino-dicyclohexyl) propane
  • MCM 3,3 4,4'-diaminodicyclohexylethane
  • T can be replaced up to 30 mol% by other dicarboxylic diacids defined above, in particular by other aromatic, aliphatic or cycloaliphatic dicarboxylic acids.
  • aromatic dicarboxylic acids may be chosen from naphthalenedicarboxylic acid (NDA) and isophthalic acid (IPS).
  • the aliphatic dicarboxylic acids may be chosen from adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanediolic acid, octadecanedioic acid and dimerized fatty acids.
  • the cycloaliphatic dicarboxylic acids may be selected from cis- and / or trans-cyclohexane-1,4-dicarboxylic acid and / or cis- and / or trans-cyclohexane-1,3-dicarboxylic acid (CHDA).
  • BAC and / or X and / or T can be replaced, independently of one another, up to
  • lactams and aminocarboxylic acids may be chosen from caprolactam (CL), ⁇ , ⁇ -aminocaproic acid, ⁇ , ⁇ -aminononanoic acid, ⁇ , ⁇ -aminoundecanoic acid (AUA) and lauryllactam (LL). and ⁇ , ⁇ -aminododecanoic acid (ADA).
  • CL caprolactam
  • ⁇ ⁇ -aminocaproic acid
  • ⁇ ⁇ -aminononanoic acid
  • LL lauryllactam
  • ADA lauryllactam
  • not more than 20 mol%, relative to the total sum of the monomers BAC, X and T may be substituted by another diamine, another diacid, a lactam or an aminocarboxylic acid or any mixture thereof is possible.
  • the present invention relates to one of the compositions for thermoplastic material No. 1 to 12 defined below, said composition comprising a semi-crystalline polyamide polymer, optionally short reinforcing fibers, said semi-crystalline polyamide polymer.
  • -crystalline comprising a BACT / XT copolyamide in the proportions defined in Table I below:
  • compositions 1 to 12 comprise from 0 to 50% by weight of additives and / or other polymers.
  • compositions consist of a semi-crystalline polyamide polymer, optionally short reinforcing fibers, and 0 to 50% by weight of additives and / or other polymers, said semi-crystalline polyamide polymer comprising a copolyamide BACT / XT in the proportions defined in Table I.
  • compositions consist of a semi-crystalline polyamide polymer, optionally short reinforcing fibers, and 0 to 50% by weight of additives and / or other polymers, said semi-crystalline polyamide polymer consisting of BACT / XT copolyamide in the proportions defined in Table I.
  • the proportion of additives and / or other polymers in the compositions defined above is more than 0 to 50% by weight.
  • X is a diamine of C 9, C 10, C 1 and C 12, in particular C 10, C 16 and C 12.
  • compositions of the invention have a better crystallization aptitude, a better compromise high Tg / low Tf and above all a higher enthalpy (and therefore higher hot modulus) than the compositions of the invention. the prior art.
  • the present invention relates to a composition as defined above, wherein said semicrystalline polyamide polymer has a melting temperature Tf ⁇ 290 ° C, preferably ⁇ 285 ° C, more preferably ⁇ 280 ° C, as determined according to ISO standard 1,1357-3 (2013).
  • the present invention relates to a composition as defined above, wherein said semicrystalline polyamide polymer has a glass transition temperature Tg> 120 ° C., preferably> 130 ° C., more preferably> 140 ° C, determined according to ISO 1,1357-2: 2013.
  • the Tg is from 125 to 165 ° C.
  • the present invention relates to a composition as defined above, wherein said semicrystalline polyamide polymer has a difference between the melting temperature and the crystallization temperature Tf-Tc ⁇ 40 ° C., preferentially ⁇ 30 ° C, determined according to ISO 1 1357-3: 2013.
  • the present invention relates to a composition as defined above, characterized in that the crystallization enthalpy of the semi-crystalline polyamide polymer, measured in Differential Scanning Calorimetry (DSC) according to ISO Standard 1 1357-3: 2013, is greater than 40 J / g, preferably greater than 45 J / g, and even more preferably 50 J / g.
  • DSC Differential Scanning Calorimetry
  • the present invention relates to a composition as defined above, characterized in that said semi-crystalline polyamide polymer has a melting temperature: Tf ⁇ 290 ° C and a Tg> 120 ° C.
  • the present invention relates to a composition as defined above, characterized in that said semi-crystalline polyamide polymer has a melting temperature: Tf ⁇ 290 ° C and a Tg> 130 ° C.
  • the present invention relates to a composition as defined above, characterized in that said semi-crystalline polyamide polymer has a melting temperature: Tf ⁇ 290 ° C and a Tg> 140 ° C.
  • the present invention relates to a composition as defined above, characterized in that said semi-crystalline polyamide polymer has a melting temperature: Tf ⁇ 285 ° C and a Tg> 120 ° C. In an advantageous embodiment, the present invention relates to a composition as defined above, characterized in that said semi-crystalline polyamide polymer has a melting temperature: Tf ⁇ 285 ° C and a Tg> 130 ° C.
  • the present invention relates to a composition as defined above, characterized in that said semi-crystalline polyamide polymer has a melting temperature: Tf ⁇ 285 ° C and a Tg> 140 ° C.
  • the present invention relates to a composition as defined above, characterized in that said semi-crystalline polyamide polymer has a melting temperature: Tf ⁇ 280 ° C and a Tg> 120 ° C.
  • the present invention relates to a composition as defined above, characterized in that said semi-crystalline polyamide polymer has a melting temperature: Tf ⁇ 280 ° C and a Tg> 130 ° C.
  • the present invention relates to a composition as defined above, characterized in that said semi-crystalline polyamide polymer has a melting temperature: Tf ⁇ 280 ° C and a Tg> 140 ° C.
  • the present invention relates to a composition as defined above, characterized in that said semi-crystalline polyamide polymer has the following characteristics (Table II):
  • composition No Initial compositions Tf (° C) Tg (° C) Tf-Tc (° C)
  • the present invention relates to a composition as defined above, characterized in that the BAC is 1, 3 BAC.
  • 1,3-BAC is a mixture of cis and trans isomers in proportion of 0/100 to 100/0, in particular 75/25 to 25/75.
  • the proportion of cis isomer in the 1.3 BAC is greater than 60%, preferably greater than 70%, in particular greater than 80%, especially greater than 90%.
  • the present invention relates to a composition as defined above, in which the BAC is 1, 3 BAC and XT is chosen from 9T, 10T, 1 1T and 12T, more preferably 10T, 1 1T. and 12T.
  • XT is 10T, 10 being 1, 10 decanediamine.
  • the present invention relates to a composition as defined above, in which the sum of the monomers which replace terephthalic acid, BAC and X is equal to 0. In this latter embodiment, it there is thus no longer possible substitution of the monomers in the compositions 1 to 93 as defined above.
  • the present invention relates to a composition as defined above, characterized in that said semi-crystalline polyamide polymer is a non-reactive composition according to b).
  • composition is the same as that of the matrix polymer (polyamide) of said thermoplastic material because there is no reaction in this composition, which remains stable and non-evolutive in terms of molecular weight during its heating for the implementation of the thermoplastic material of the invention.
  • the characteristics of the polyamide polymer in this composition are the same, with Tf, Tg, Tf-Tc and Delta Hc as defined above as those of the final polymer.
  • the polyamides according to b) are obtained by conventional polycondensation reaction from monomeric components which are diamines, diacids and optionally amino acids or lactams, especially in the context of substitution of the monomers.
  • the present invention relates to a composition as defined above, characterized in that said polyamide composition is a reactive prepolymer composition according to a) and precursor of said polyamide polymer of said matrix of thermoplastic material.
  • said composition a) comprises or consists of at least one carrier reactive prepolymer on the same chain of two terminal functions X 'and Y', functions respectively coreactive between them by condensation, with X 'and Y' being amine and carboxyl or carboxyl and amine respectively.
  • the prepolymer is a reactive polyamide carrying on the same chain (that is to say on the same prepolymer) two terminal functions X 'and Y' functions respectively coreactive to each other by condensation.
  • This condensation reaction can cause the elimination of by-products.
  • These can be removed by preferably working in a method using open mold technology.
  • a step of degassing, preferably under vacuum, by-products removed by the reaction is present, this in order to avoid the formation of microbubbles by-products in the final thermoplastic material , which (microbubbles) can affect the mechanical performance of said material if they are not removed as well.
  • the characteristics of the final polyamide polymer obtained in this composition are the same, with Tf, Tg, Tf-Tc and Delta Hc as defined above.
  • said reactive composition a) comprises at least two polyamide prepolymers reactive with each other and each bearing two identical terminal functions X 'or Y' respectively, said function X 'of a prepolymer being able to react only with said function Y' of the other prepolymer, in particular by condensation, more particularly with X 'and Y' being amine and carboxyl or carboxyl and amine respectively.
  • this condensation (or polycondensation) reaction can cause the elimination of by-products which can be removed as defined above.
  • the characteristics of the final polyamide polymer obtained in this composition are the same, with Tf, Tg, Tf-Tc and Delta Hc as defined above.
  • composition a) or precursor composition comprises or consists of:
  • thermoplastic polyamide polymer carrying n terminal functional functions X ', chosen from: -IMH2, -CO2H and -OH, preferably NH2 and -CO2H with n being 1 to 3, preferably from 1 to 2, more preferably 1 or 2, more particularly 2
  • a2) at least one Y-A'-Y chain extender, with A 'being a hydrocarbon biradical, of non-polymeric structure, carrying 2 identical Y terminal reactive functional groups reactive by polyaddition with at least one X' function of said prepolymer a1 ), preferably of molecular weight less than 500, more preferably less than 400.
  • elongators a2) as a function of the functions X 'carried by said semi-crystalline polyamide prepolymer a1), the following may be mentioned: when X 'is NH2 or OH, preferably NH2:
  • ⁇ Y chosen from the groups: maleimide, optionally blocked isocyanate, oxazinone, oxazolinone and epoxy,
  • a ⁇ A ' is a hydrocarbon spacer optionally comprising one or more heteroatoms, and connecting functions Y therebetween, in particular A is a hydrocarbon spacer or a carbonaceous radical bearing functions or reactive groups Y, selected from:
  • the chain extender Y-A'-Y corresponds to Y being a caprolactam group and to A 'may be a carbonyl radical such as carbonyl biscaprolactam or A may be a terephthaloyl or isophthaloyl, o is said elongator of Y-A'-Y chain carries a group Y of cyclic anhydride and preferably this elongator is chosen from a cycloaliphatic and / or aromatic carboxylic dianhydride and more preferably it is chosen from: ethylenetetracarboxylic dianhydride, pyromellitic dianhydride, dianhydride 3 , 3 ', 4,4'-biphenyltetracarboxylic, 1,5,5,8-naphthalenetetracarboxylic dianhydride, perylenetetracarboxylic dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic dianhydride,
  • said chain extender Y-A'-Y corresponds to: ⁇ Y chosen from the groups: epoxy, oxazoline, oxazine, imidazoline or aziridine such as 1, 1 '-iso- or terephthalic phthaloyl-bis (2-methyl aziridine)
  • ⁇ A ' is a spacer (group) carbon as defined above.
  • this blocking can be obtained by blocking agents of the isocyanate function, such as epsilon-caprolactam, methyl ethyl ketoxime, dimethyl pyrazole, diethyl malonate.
  • blocking agents of the isocyanate function such as epsilon-caprolactam, methyl ethyl ketoxime, dimethyl pyrazole, diethyl malonate.
  • the preferred conditions avoid any formation of imide ring during the polymerization and during the implementation at the same time. melted state.
  • aliphatic diepoxides are diglycidyl ethers of aliphatic diols, aromatic diepoxides of diglycidyl ethers of bisphenol A such as diglycidyl ether of bisphenol A (DGEBA) and cycloaliphatic diepoxides, diglycidyl ethers of cycloaliphatic diols or bisphenol.
  • DGEBA diglycidyl ether of bisphenol A
  • cycloaliphatic diepoxides diglycidyl ethers of cycloaliphatic diols or bisphenol.
  • diepoxides More generally, as suitable examples of diepoxides according to the invention, mention may be made of bisphenol A diglycidyl ether (DGEBA) and its hydrogenated derivative (cycloaliphatic), bisphenol F diglycidyl ether, tetrabromo bisphenol A diglycidyl ether or hydroquinone diglycidyl ether ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, butylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, polyethylene glycol diglycidyl ether Mn ⁇ 500, polypropylene glycol diglycidyl ether of Mn ⁇ 500, polytetramethylene glycol diglycidyl
  • chain extenders carrying oxazoline or oxazine reactive functions Y that are suitable for the implementation of the invention, reference may be made to those described under references “A”, “B”, “C” and “D”. on page 7 of application EP 0 581 642, as well as to their preparation processes and their reaction modes which are exposed to them.
  • "A” in this document is bisoxazoline, "B” bisoxazine, "C” 1, 3 phenylene bisoxazoline and "D" 1,4-phenylene bisoxazoline.
  • Y-imidazoline reactive chain extenders suitable for the implementation of the invention, reference may be made to those described ("A" to "F") on pages 7 to 8 and Table 1 of the page 10 in the application EP 0 739 924 as well as their processes of preparation and their modes of reaction which are exposed to it.
  • Y oxazinone or oxazolinone reactive functional chain extenders which are suitable for the implementation of the invention, reference may be made to those described under references “A” to "D” on pages 7 to 8 of EP 0 581 641, and to their preparation processes and their reaction modes which are exposed to them.
  • groups Y oxazinones (6-atom ring) and oxazolinones (5-atom ring) are suitable Y groups derived from: benzoxazinone oxazinone or oxazolinone, with as spacer A 'can be a single bond covalently with respective corresponding lengtheners being: bis- (benzoxazinone), bisoxazinone and bisoxazolinone.
  • a ' may also be a C1 to C4 alkylene, preferably a C2 to C10 alkylene, but preferably A' is an arylene and more particularly it may be a phenylene (substituted with Y at the 1, 2 or 1, 3 or 1 positions, 4) or a naphthalene radical (disubstituted by Y) or phthaloyl (iso- or terephthaloyl) or A 'may be a cycloalkylene.
  • the radical A ' can be as described above with A' being a simple covalent bond and with the extenders respective corresponding ones being: bisoxazine, bisoxazoline and bisimidazoline.
  • A may also be a C1 to C14 alkylene, preferably a C2 to C10 alkylene.
  • the radical A ' is preferably an arylene and, more particularly, it may be a phenylene (substituted with Y in the 1, 2 or 1, 3 or 1, 4 positions) or a naphthalene (disubstituted by Y) or phthaloyl radical ( iso- or terephthaloyl) or A 'may be cycloalkylene.
  • the radical A ' may be a phthaloyl (1, 1' iso). or terephthaloyl) with, as an example of such an extender, isophthaloyl-bis (2-methyl aziridine).
  • a catalyst for the reaction between said P (X ') n prepolymer and said Y-A'-Y extender at a level ranging from 0.001 to 2%, preferably from 0.01 to 0.5% relative to the total weight of two co-reactants mentioned can accelerate the reaction of (poly) addition and thus shorten the production cycle.
  • a ' may represent an alkylene, such that - (Chb - with m ranging from 1 to 14 and preferably from 2 to 10 or represents a substituted arylene alkyl or unsubstituted, such as arylenes benzenes (such as o-, m-, -p) or naphthalenic phenylenes (with arylenes: naphthalenylenes)
  • arylenes benzenes such as o-, m-, -p
  • naphthalenic phenylenes with arylenes: naphthalenylenes
  • a ' represents an arylene which may be substituted or unsubstituted benzene or naphthenic.
  • said chain extender (a2) has a non-polymeric structure and preferably a molecular weight less than or equal to 500, more preferably less than or equal to 400.
  • Said reactive prepolymers of said reactive composition a), according to the three options mentioned above, have a number-average molecular mass Mn ranging from 500 to 10,000, preferably from 1000 to 6000. All masses Mn are determined by potentiometry or by NMR. (Postma et al (Polymer, 47, 1899-191 1 (2006)).
  • said reactive prepolymers are prepared by conventional polycondensation reaction between the corresponding diamine and diacid components and optionally (depending on the substitutions) amino acids or lactams.
  • the prepolymers bearing X 'and Y' amino and carboxyl functions on the same chain can be obtained for example by adding a combination of monomers (amino acid, diamine, diacid) having in total an equal amount of amino and carboxyl units, but not not conducting the reaction until total conversion.
  • n 3 for example, for a prepolymer P (X ') n, the presence of a trifunctional component is required, for example the presence of a triamine (one mole per prepolymer chain) with a diamine in the reaction with a diacid.
  • the present invention relates to a composition as defined above, said composition a) or precursor composition, comprising or consisting of:
  • thermoplastic polyamide polymer carrying n terminal functional functions X '
  • X ' is Nhb or OH, in particular NH 2 and Y is chosen from an anhydride, in particular 3,3', 4,4'-benzophenone tetracarboxylic dianhydride, an oxazinone, an oxazolinone and an epoxy
  • the present invention relates to a composition as defined above, said composition a) or precursor composition, comprising or consisting of:
  • thermoplastic polyamide polymer carrying n terminal functional functions X '
  • X ' is CO2H and Y is selected from epoxy and oxazoline.
  • X ' is CO2H and Y-A'-Y is chosen from bis oxazoline phenylenes, preferably 1,3-phenylenebis (2-oxazoline) or 1,4-phenylenebis (2-oxazoline). (PBO).
  • the present invention relates to a composition as defined above, characterized in that it comprises a1) at least one amine prepolymer (carrier of -NH2), of said thermoplastic polymer of the matrix , in particular with at least 50% and more particularly with 100% of the end groups of said prepolymer a1) being primary amine functions -NH2 and a2) at least one chain extender, non-polymeric and carrying a cyclic carboxylic anhydride group, preferably carried by an aromatic ring, having as a substituent a group comprising ethylenic or acetylenic unsaturation, preferably acetylenic, said carboxylic anhydride group may be in acid, ester, amide or imide form with said extension a2) being present at a level corresponding to a molar ratio a2) / (-NH2) less than 0.36, preferably ranging from 0.1 to 0.35, more preferably ranging from 0.15 to 0.35 and even more preferentially ranging from from from
  • thermoplastic final polymer which is not crosslinked.
  • Said prepolymer a1) carries primary amine groups represented by -NH2. More particularly, it should be noted that the average number of primary amine groups per molecule of prepolymer a1), ie the average functionality in primary amine groups, can vary from 1 to 3 and preferably from 1 to 2. In particular, the functionality of said prepolymer a1) at least 50% of the end groups of said prepolymer a1) being primary amine functions -NH2, this means that it is possible for a part to be carboxyl groups or chain ends blocked without grouping reagent and in this case, the average functionality in -NH2 can thus vary from 1 to 3 and preferably from 1 to 2.
  • thermoplastic in the case of the present invention means that the polymer resulting from the reaction of the prepolymer a1) and the extender a2) is essentially thermoplastic, which means that it contains less than 15% of its weight. preferably less than 10% of its weight and more preferably less than 5% of its weight and even more preferably 0% of its weight (to within 0.5% or within 1%) of crosslinked polymers which are insoluble or infusible .
  • Said extender a2) can be chosen from:
  • ethynyl isophthalic methyl ethynyl isophthalic, phenyl ethynyl isophthalic, naphthyl ethynyl isophthalic, 4- (o-phthaloyl ethynyl) isophthalic, 4- (phenyl ethynyl ketone) isophthalic, ethynyl terephthalic, methyl ethynyl terephthalic, phenyl ethynyl terephthalic acid, naphthyl ethynyl terephthalic acid, 4- (o- phthaloyl ethynyl) terephthalic acid, ethynyl benzoic acid, methyl ethynyl benzoic acid, phenyl ethynyl benzoic acid, naphthyl ethynyl benzoic acid, naphthyl
  • said extender a2) is chosen from aromatic anhydride compounds, preferably o-phthalic, substituted at the 4-position of the aromatic ring by a substituent defined by a group R-C5C- (R ') x- with R being an alkyl C1-C2 or H or aryl, in particular phenyl or R is the residue of an aromatic carboxylic anhydride, preferably o-phthalic, linked to the acetylenic triple bond by the carbon at the 4-position of the aromatic ring and x being equal to 0 or at 1 and for x being 1, R 'being a carbonyl group.
  • aromatic anhydride compounds preferably o-phthalic, substituted at the 4-position of the aromatic ring by a substituent defined by a group R-C5C- (R ') x- with R being an alkyl C1-C2 or H or aryl, in particular phenyl or R is the residue of an aromatic carboxylic anhydride, preferably o-phthalic
  • said elongator a2) is chosen from o-phthalic aromatic anhydride compounds bearing in the 4-position a substituent group chosen from methyl ethynyl, phenyl ethynyl, 4- (o-phthaloyl) ethynyl, phenyl ethynyl ketone, also known as phenyl ethynyl anhydride. trimellitic and preferably carriers in the 4-position of a substituent group selected from methyl ethynyl and phenyl ethynyl ketone.
  • said extender a2) as defined above and whatever its structure, has a molecular weight less than or equal to 500, preferably less than or equal to 400.
  • the level of said extender a2), as defined above and whatever its structure, in said polyamide polymer ranges from 1 to 20%, in particular from 5 to 20%.
  • the present invention relates to a composition as defined above, characterized in that it is a molding composition.
  • the present invention relates to a process for manufacturing a thermoplastic material, in particular a mechanical part or a structural part based on said material, of composition as defined above, characterized in that it comprises at least one step of polymerization of at least one reactive composition a) as defined above according to the invention or a molding step or implementation of at least one non-reactive composition b) such as defined above, by extrusion, injection or molding.
  • the present invention relates to a method for manufacturing a thermoplastic material as defined above, characterized in that it comprises the following steps:
  • the present invention relates to a semi-crystalline polyamide polymer, characterized in that it corresponds to (or is) the polymer of the thermoplastic matrix of said thermoplastic material, as defined above, said polymer being a polymer non-reactive as defined according to said composition b) or a polymer obtainable from a reactive composition as defined according to said composition a).
  • thermoplastic polymer is by definition one of the essential components of the composition of the thermoplastic material of the present invention and is therefore part of the invention as a product related to the present invention with the same common inventive concept facing the same technical problem to solve.
  • the invention thus also covers the use of said thermoplastic polymer according to the invention as a thermoplastic matrix of a thermoplastic material based on a fibrous reinforcement as described above.
  • the present invention relates to the use of a composition as defined above or of a non-reactive polymer as defined according to said composition b) or a polymer that can be obtained from a reactive composition as defined according to said composition a), for the manufacture of mechanical or structural parts, based on said thermoplastic material, single-layer or multilayer pipe, or film
  • the present invention relates to the use as defined above, characterized in that said mechanical or structural parts of said thermoplastic material relate to applications in the field of automotive, railway, marine (marine), wind, photovoltaic, solar, including solar panels and components of solar power plants, sports, aeronautics and space, road transport (for trucks), building, civil engineering , signs and hobbies.
  • the present invention relates to the use as defined above, characterized in that said mechanical parts for automotive applications are parts under the bonnet for the transport of fluid, particularly in air intake devices, cooling (for example by air, coolant, etc.), transport or transfer of fuels or fluids, in particular oil, water, etc.
  • the present invention relates to the use as defined above, characterized in that said mechanical or structural parts for electrical or electronic applications are equipment items.
  • electrical and electronic such as encapsulated solenoids, pumps, telephones, computers, printers, fax machines, modems, monitors, remote controls, cameras, circuit breakers, electrical cable ducts, fiber optics, switches, multimedia systems.
  • the present invention relates to a thermoplastic material resulting from the use of at least one composition for thermoplastic material as defined above.
  • the present invention relates to a mechanical part or structure of thermoplastic material, resulting from the use of at least one composition as defined above or the use of a polyamide polymer as defined herein. above or that it is based on a material as defined above or that it is obtained by a method as defined above.
  • the part defined above is a mechanical part for applications in the automobile such as parts under the engine hood for the transport of fluid, in particular in air intake devices, cooling (for example by air, coolant, etc.), transport or transfer of fuels or fluids (such as oil, water, etc.).
  • the part is a mechanical or structural part for electrical or electronic applications such as electrical and electronic equipment, such as encapsulated solenoids. , pumps, telephones, computers, printers, fax machines, modems, monitors, remote controls, cameras, circuit breakers, electrical cable ducts, fiber optics, switches, multimedia systems. Methods of determining the characteristics quoted
  • the glass transition temperature Tg is measured using a differential scanning calorimeter (DSC), after a second heat-up, according to the ISO 1 1357-2: 2013 standard.
  • the heating and cooling rate is 20 ° C / min.
  • the melting temperature Tf and the crystallization temperature Te are measured by DSC, according to the standard ISO 1,1357-3: 2013.
  • the heating and cooling speed is
  • the module E 'at 180 ° C is obtained from dynamic mechanical analysis curves (DMA) carried out on bars in voltage mode, using a ramp of 2 ° C / min, a frequency of 1 Hz and amplitude of 10 ⁇ .
  • DMA dynamic mechanical analysis curves
  • the Mn of the prepolymer is determined from the titration (assay) of the COOH or NH 2 terminal functions according to a potentiometric method and from a theoretical functionality of 2.
  • Figure 1 shows the curves of Tf, Tg, Te and Delta Hc obtained as a function of the molar percentage of BACT in a copolyamide BACT / 10T.
  • the monofunctional chain regulator benzoic acid in an amount adapted to the target Mn and variant (benzoic acid) of 50 to 100 g,
  • the sealed reactor is purged of its residual oxygen and then heated to a temperature of 230 ° C with respect to the material introduced. After stirring for 30 minutes under these conditions, the pressurized steam which has formed in the reactor is gradually relieved in 60 minutes, while progressively increasing the material temperature so that it is established at Tf + 10. ° C at atmospheric pressure.
  • the polymerization is then continued under a nitrogen sweep of 20 l / h until the target mass Mn indicated in the table of characteristics is obtained.
  • the polymer is then drained by the bottom valve and then cooled in a water tank and then granulated.
  • the Tg is very high and can be modulated from 125 ° C (not shown in the table) to about 165 ° C.
  • the enthalpy of crystallization for all these products is particularly high, and especially greater than 50J / g (especially greater than the MXDT / 10T described in WO 2014/064375).
  • the closed reactor is purged of its residual oxygen and then heated to a temperature of 230 ° C of the material. After stirring for 30 minutes under these conditions, the pressurized steam which has formed in the reactor is gradually relieved in 60 minutes, while progressively increasing the material temperature so that it is established at Tf + 10. ° C at atmospheric pressure.
  • the oligomer (prepolymer) is then drained by the bottom valve and then cooled in a water tank and ground.
  • the mixture is left under recirculation in the micro-extruder and the increase in viscosity is monitored by measuring the normal force. After about 15 minutes, the contents of the micro-extruder are drained in the form of a rod. The air-cooled product is granulated.
  • the product 112 obtained has an inherent viscosity of 1.92.
  • the resulting product 113 has an inherent viscosity of 0.97.

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EP17745845.2A 2016-07-11 2017-07-10 Halbkristalline polyamidzusammensetzung mit einer hohen glasübergangstemperatur für ein thermoplastisches material, herstellungsverfahren dafür und verwendungen davon Pending EP3325537A1 (de)

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FR1656624A FR3053695B1 (fr) 2016-07-11 2016-07-11 Composition de polyamide semi-cristallin de haute temperature de transition vitreuse pour materiau thermoplastique, son procede de fabrication et ses utilisations
PCT/FR2017/051872 WO2018011494A1 (fr) 2016-07-11 2017-07-10 Composition de polyamide semi-cristallin de haute temperature de transition vitreuse pour matériau thermoplastique, son procede de fabrication et ses utilisations

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JP2018531296A (ja) 2018-10-25
CN108026267A (zh) 2018-05-11
US20190040198A1 (en) 2019-02-07
CN108026267B (zh) 2021-02-02
KR20180032651A (ko) 2018-03-30
WO2018011494A1 (fr) 2018-01-18
KR101944680B1 (ko) 2019-01-31
US10633490B2 (en) 2020-04-28
FR3053695B1 (fr) 2018-07-06
JP6526911B2 (ja) 2019-06-05

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