EP2556104A1 - High-viscosity polyamide composition - Google Patents

High-viscosity polyamide composition

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Publication number
EP2556104A1
EP2556104A1 EP11711914A EP11711914A EP2556104A1 EP 2556104 A1 EP2556104 A1 EP 2556104A1 EP 11711914 A EP11711914 A EP 11711914A EP 11711914 A EP11711914 A EP 11711914A EP 2556104 A1 EP2556104 A1 EP 2556104A1
Authority
EP
European Patent Office
Prior art keywords
acid
amine
composition according
bis
polyamide
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.)
Ceased
Application number
EP11711914A
Other languages
German (de)
French (fr)
Inventor
Magali Davezac
Wojciech Bzducha
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Performance Polyamides SAS
Original Assignee
Rhodia Operations SAS
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Filing date
Publication date
Application filed by Rhodia Operations SAS filed Critical Rhodia Operations SAS
Publication of EP2556104A1 publication Critical patent/EP2556104A1/en
Ceased legal-status Critical Current

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    • 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
    • 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
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic 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
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C08G69/12—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids with both amino and carboxylic groups aromatically bound
    • 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
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C08G69/14—Lactams
    • 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
    • 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
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • 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
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/002—Dendritic macromolecules
    • C08G83/003—Dendrimers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/005—Dendritic macromolecules
    • 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
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L35/06—Copolymers with vinyl aromatic monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Definitions

  • the present invention relates to a high viscosity polyamide composition comprising a branched polyamide. It relates more particularly to a composition comprising a random tree type copolyamide resulting from the reaction between a multifunctional monomer comprising at least three reactive functions to form an amide function, these functions being of two different types, and bifunctional monomers conventionally used in the manufacture linear polyamides.
  • the copolyamide obtained has a very low melt flow index relative to the linear polyamide and improved impact properties.
  • the invention also relates to the use of this composition for the extrusion blow molding of articles. In the field of parts made of plastic, many parts are obtained by molding a composition comprising as matrix a polyamide.
  • the polyamides generally used are linear aliphatic, aromatic or semi-aromatic polyamides.
  • the new processes for shaping these compositions such as, for example, extrusion blow molding, require compositions having a high melt viscosity so that the extruded part before blowing does not deform or weakly under the effect of its extrusion. own weight.
  • the mechanical, elastic and impact properties of the parts must not be affected or weakly affected.
  • the object of the invention is a new polyamide having a high melt viscosity, which can be obtained by a simple and controllable manufacturing process and with satisfactory mechanical characteristics, without penalize the different properties of use of manufactured articles, such as in particular the permeability.
  • the present invention provides a composition obtainable by mixing at least: a) a random tree type structure copolyamide which is the result of the reaction between at least:
  • n is an integer from 2 to 10 (inclusive)
  • R1, R2 may be the same or different and represent a covalent bond, an aliphatic, arylaliphatic, aromatic or alkylaromatic hydrocarbon radical
  • R is a linear aliphatic radical or branched, a substituted or unsubstituted cycloaliphatic radical, a substituted or unsubstituted aromatic radical which may comprise several aromatic nuclei and / or heteroketones
  • A represents the amine or amine salt function, or the acid, ester, acid halide or amide function
  • B represents the amine or amine salt function when A represents an acid, ester, acid halide or amide function
  • an acid, ester, acid halide or amide function when A represents an amine or salt function.
  • amine at least one of the following bifunctional monomers of formulas II to IV:
  • Ai, B1 respectively represent an acid, ester or acid chloride function, and an amine function, or an amine salt
  • R3, R4, R5, RQ, RJ represent linear or branched alkyl hydrocarbon radicals, substituted aromatic or non-alkylaryl, arylalkyl or cycloaliphatic radicals which may comprise unsaturations
  • b) a chain extender
  • the radical R is an aromatic radical, R ⁇
  • the functions B and A of the formula (I) are respectively an acid function and an amine function, the number n of acid function being advantageously equal to 2.
  • the preferred and preferred polyfunctional monomers of the invention are, in particular, the thermally stable monomers at a temperature above 150 ° C.
  • R represents an aromatic radical such as aminophthalic acid, or a linear aliphatic radical such as 3-aminopimelic diacid, or the acid 6-amino undecandioic acid Mention may also be made of ⁇ -amino acids such as aspartic acid or glutamic acid. Natural amino acids can also be used as a polyfunctional monomer if their thermal stability is sufficient.
  • the difunctional monomers of formulas (II) to (IV) are the monomers used for the manufacture of linear thermoplastic polyamide.
  • ⁇ -aminoalkanoic compounds comprising a hydrocarbon chain containing from 4 to 12 carbon atoms, or the lactams derived from these amino acid acids such as ⁇ -caprolactam, the saturated aliphatic carboxylic diacids containing from 6 to 12 carbon atoms such as that, for example, adipic acid, azelaic acid, sebacic acid, dodecanoic acid, preferably linear or branched saturated aliphatic biprimary diamines having from 6 to 12 atoms carbon such as, for example, hexamethylenediamine, trimethylhexamethylenediamine, tetramethylenediamine, m-xylene diamine.
  • the preferred bifunctional monomers of the invention are ⁇ -caprolactam, or hexamethylenediamine and adipic acid or a mixture thereof.
  • the molar ratio between the multifunctional monomers of formula (I) and the sum of the bifunctional monomers of formulas (II) to (IV) and monofunctional monomers of formulas (V) and (VI) is preferably between 0.01% and 5% preferably between 0.05% and 1% to obtain a copolyamide having a level of mechanical properties equivalent to that of the corresponding linear polyamide.
  • the copolyamide preferably has a melt flow index (MFI) of less than 5 g / 10 min (measured at 275 ° C under a load of 2160 g), and preferably a molecular weight distribution index D of greater than 2.
  • MFI melt flow index
  • the distribution index D of the molecular masses is a function of the degree of polymerization DPn and the factor of functionality F of the polymer.
  • the polymerization is in particular carried out according to the conventional operating conditions of polymerization of dicarboxylic acids and diamines, when this is carried out in the absence of multifunctional compounds.
  • Such a polymerization process may briefly include:
  • the polymerization can be perfectly carried out until the thermodynamic equilibrium of the polyamide is obtained.
  • the multifunctional and optionally monofunctional compounds are preferably added at the beginning of the polymerization.
  • the polymerization of a mixture of dicarboxylic and diamine monomers and multifunctional and monofunctional compounds is carried out.
  • additives such as, for example, catalysts, such as, in particular, phosphorus catalysts, antifoam agents, and agents that stabilize light or heat.
  • the polymer At the polymerization outlet, the polymer can be cooled advantageously with water, and extruded and cut to produce granules.
  • the polymerization process according to the invention can perfectly be carried out continuously or discontinuously.
  • the chain extenders of the polyamide are usually capable of reacting with the end groups of the amino or acidic polyamide.
  • the chain extenders have at least two functions capable of reacting with the end groups of the polyamide so as to connect two polyamide chains and thus increase the viscosity of the modified polyamide.
  • the use of bis-lactams is especially mentioned in US Pat. No. 2,682,526.
  • chain extenders As chain extenders according to the invention, mention may especially be made of compounds chosen from the group consisting of: dialcohols such as ethylene glycol, propane diol, butane diol, hexane diol, hydroquinone-bis-hydroxyethyl ether, bis epoxides such as diglicydyl ether of bisphenol A, Polymers carrying epoxide functions, polymers bearing anhydride functions, bis-N-acyl bis-caprolactams, such as isophthaloyl bis-caprolactam (IBC), adipoyl bis-caprolactam (ABC), terphthaloyl bis-caprolactam (TBC), diphenyl carbonates, bisoxazolines, oxazolinones, diisocyanates, organic phosphites, such as tri phenyl phosphite, caprolactam phosphite, bis ketenimines, dianhydrides.
  • the composition preferably comprises from 0.01 to 5% by weight of chain extenders of the polyamide, relative to the total weight of the composition. More preferentially, the composition comprises from 0.1 to 3% by weight of chain extenders of the polyamide, relative to the total weight of the composition. In particular, 0.01 to 10% by weight of chain extenders of the polyamide may be used, relative to the weight of the polyamide.
  • Preferred extender chains are insensitive to the moisture content of the polyamide under the conditions of the polyamidation reaction, and do not generate byproducts.
  • At least one reinforcing and / or filling filler preferentially chosen from the group comprising fibrous fillers such as glass fibers, mineral fillers such as clays. , kaolin, or reinforcing nanoparticles or thermo-hardenable material, and powder fillers such as talc.
  • the rate of incorporation in reinforcing and / or filling load is in accordance with the standards in the field of composite materials. It may be for example a charge rate of 1 to 80%, preferably 10 to 70%, especially between 30 and 60%.
  • composition may comprise, in addition to the modified polyamide of the invention, one or more other polymers, preferably polyamides or copolyamides.
  • composition according to the invention may further comprise additives usually used for the manufacture of polyamide compositions for to be molded.
  • additives usually used for the manufacture of polyamide compositions for to be molded may be made of lubricants, flame-retardants, plasticizers, nucleating agents, catalysts, resilience-improving agents such as optionally grafted elastomers, light and / or thermal stabilizers, antioxidants, antistats, dyes, matifying agents, molding aid additives or other conventional additives.
  • fillers and additives may be added to the modified polyamide by conventional means suitable for each filler or additive, such as for example during the polymerization or in cold or melt blending.
  • composition according to the invention comprising the polyamide as defined above may also comprise at least one impact modifier, that is to say a compound capable of modifying the impact resistance of a polyamide composition.
  • shock-modifying compounds preferably comprise functional groups that are reactive with the polyamide.
  • polyamide-reactive functional groups are understood to mean groups capable of reacting or chemically interacting with the acidic or amine functional groups of the polyamide, in particular by covalence, ionic interaction or hydrogen or van der Walls bonding. Such reactive groups make it possible to ensure good dispersion of the impact modifiers in the polyamide matrix. Good dispersion is generally obtained with particles of impact modifying agents having an average size of between 0.1 and 1 ⁇ in the matrix.
  • Shock modifiers comprising functional groups reactive with the polyamide are preferably used depending on the acid or amine nature of the ⁇ of the polyamide.
  • the ⁇ is acidic, it will be preferable to use reactive functional groups capable of reacting or chemically interacting with the acid functions of the polyamide, in particular by covalence, ionic interaction or hydrogen or van der Walls bonding.
  • the ⁇ is amine, it will be preferable to use reactive functional groups capable of reacting or chemically interacting with the amine functions of the polyamide, in particular by covalence, ionic interaction or hydrogen or van der Walls bonding.
  • Shock modifiers having functional groups reactive with the polyamide having an ⁇ of amine nature are preferably used.
  • shock-modifying agents can very well comprise functional groups reactive with the polyamide, for example with regard to acrylic acid ethylenes (EAA).
  • EAA acrylic acid ethylenes
  • the impact modifying agents which are compounds, oligomeric or polymeric, comprising at least one of the following monomers, or their mixture: ethylene, propylene, butene, isoprene, diene, acrylate, butadiene, styrene, octene, acrylonitrile, acrylic acid, methacrylic acid, vinyl acetate, vinyl esters such as acrylic and methacrylic esters and glycidyl methacrylate.
  • These compounds according to the invention may also comprise in addition to other monomers than those mentioned above.
  • the base of the impact-modifying compound can be chosen from the group comprising: polyethylenes, polypropylenes, polybutenes, polyisoprenes, ethylene-propylene rubbers (EPR), ethylene-rubbers, propylene-diene (EPDM), ethylene and butene rubbers, ethylene and acrylate rubbers, butadiene and styrene rubbers, butadiene and acrylate rubbers, ethylene and octene rubbers , butadiene acrylonitrile rubbers, ethylene acrylic acid (EAA), ethylene vinyl acetate (EVA), ethylene acrylic ester (EEA), acrylonitrile copolymers butadiene styrene (ABS), styrene ethylene butadiene styrene block copolymers (SEBS), styrene butadiene styrene copolymers (SBS), core-shell methacrylate
  • EAA ethylene acrylic acid
  • shock-modifying agents can also comprise, generally grafted or copolymerized, functional groups that are reactive with the polyamide, such as in particular the following functional groups: acids, such as carboxylic acids, acids salified esters in particular, acrylates and methacrylates, ionomers, glycidyl groups including epoxy, glycidyl esters, anhydrides including maleic anhydrides, oxazolines, maleimides, or mixtures thereof.
  • Such functional groups on the elastomers are for example obtained by using a comonomer during the preparation of the elastomer.
  • impact-modifying agents comprising functional groups that are reactive with the polyamide
  • terpolymers of ethylene, acrylic ester and glycidyl methacrylate copolymers of ethylene and butyl ester acrylate, copolymers of ethylene, n-butyl acrylate and glycidyl methacrylate, copolymers of ethylene and maleic anhydride, styrene-maleimide copolymers grafted with maleic anhydride, styrene-ethylene-butylene-styrene copolymers modified with maleic anhydride, styrene-maleic anhydride copolymers, acrylonitrile grafted maleic anhydrides, acrylonitrile butadiene styrene copolymers grafted maleic anhydrides, and their hydrogenated versions.
  • the proportion by weight of the impact-modifying agents in the total composition is in particular between 0.1 and 50%, preferably between 0.1 and 20%, especially between 0.1 and 10%, relative to the total weight of the composition. .
  • the composition according to the present invention preferably comprises a random tree structure copolyamide, a chain extender and a shock modifier.
  • the compositions of the invention are obtained by generally mixing in a single or twin-screw extruder, a polyamide according to the invention with the various additives, this mixture being generally carried out in the molten state. polyamide, then extrusion of the mixture in the form of rods which are then cut into granules. The molded parts are then made by melting the granules produced above and supplying the composition in the molten state into the appropriate molding, injection or extrusion devices.
  • the composition according to the invention can be used in many applications such as the manufacture of molded or injected or blown parts.
  • the composition is particularly suitable for the manufacture of parts by continuous or discontinuous extrusion blow molding techniques, with or without an accumulation head. Indeed, the low melt fluidity of the composition makes it possible to limit the deformations of the parisons during their extrusion, before the blowing step.
  • the present invention also relates to an extrusion blow molding process using a polyamide composition according to the invention.
  • composition according to the invention can also also be used as a matrix in a composition comprising a high proportion of masterbatch additives intended to be mixed with another thermoplastic composition.
  • compositions of the invention may also comprise, as polymeric matrix, in addition to the polyamide as described above, other thermoplastic materials such as linear aliphatic polyamides or aromatic or semi-aromatic polyamides, for example.
  • the compounds used are the following:
  • the polyamide has a melt flow index (MFI) of 5 to 10 g / 10 min (according to ASTM D1238 under a load of 2160 g and at a temperature of 275 ° C); and a viscosity index of 200 to 225 ml / g (determined in formic acid according to the method PN-EN ISO 307)
  • Linear polyamide 66 having an IV of 175 ml / g (determined in 90% formic acid according to ISO 307)
  • chain extender Araldite GT7071, SMA Xiran XZ-09-002 (Polyscope) (copolymer of styrene with maleic anhydride))
  • Exxelor VA1801 maleic anhydride grafted ethylenic copolymer
  • the extrusion parameters are as follows: extrusion temperature with increasing profile 250-270 ° C; speed of rotation of the screw: 250 rpm; flow rate of the composition 40 kg / h; the engine torque and the engine power absorbed vary depending on the polyamides. Table 1
  • the notched Charpy impact is measured according to ISO 179-1 / 1 eA.
  • the viscosity is measured using a Gottfert capillary rheometer 2002.
  • a piston moving at programmed speeds pushes the molten polymer through a capillary of length L (30 mm) and diameter D (1 mm).
  • the corresponding flow rate is measured from which the apparent viscosity can be deduced.
  • a shear rate sweep is performed from 5000 s -1 to 10 s -1 .
  • the melt strenght is measured in the following manner: the polymer formulated in a single screw blowing machine is introduced at a temperature profile of 250-275 ° C. and at a fixed screw speed of 40 rpm; and the time required to allow the parison of molten polymer to travel a distance of 75 cm is recorded with the aid of photocells. The measurement is repeated at least 5 times in order to check the standard low deviation.

Abstract

The present invention relates to a high-viscosity polyamide composition including a branched polyamide. Said invention relates specifically to a composition including a copolyamide of the statistical tree type resulting from the reaction between a multifunctional monomer including at least three reactive functions in order to form an amide function, said functions being of two different types, and bifunctional monomers conventionally used in the manufacture of linear polyamides. The resulting copolyamide has a very low melt flow index relative to the linear polyamide and improved impact resistance properties. The invention also relates to the use of said composition for extrusion blow-molding articles.

Description

COMPOSITION POLYAMIDE DE HAUTE VISCOSITE  POLYAMIDE COMPOSITION OF HIGH VISCOSITY
La présente invention concerne une composition polyamide de haute viscosité comprenant un polyamide branché. Elle concerne plus particulièrement une composition comprenant un copolyamide du type arbre statistique résultant de la réaction entre un monomère plurifonctionnel comprenant au moins trois fonctions réactives pour former une fonction amide, ces fonctions étant de deux types différents, et des monomères bifonctionnels classiquement utilisés dans la fabrication des polyamides linéaires. Le copolyamide obtenu présente un indice de fluidité en fondu très faible par rapport au polyamide linéaire et des propriétés de résistance aux chocs améliorées. L'invention concerne également l'utilisation de cette composition pour l'extrusion soufflage d'articles. Dans le domaine des pièces réalisées en matière plastique, de nombreuses pièces sont obtenues par moulage d'une composition comprenant comme matrice un polyamide. Les polyamides généralement utilisés sont des polyamides linéaires aliphatiques, aromatiques ou semi-aromatiques. Les nouveaux procédés de mise en forme de ces compositions, comme par exemple, l'extrusion-soufflage requièrent des compositions présentant une viscosité en milieu fondu élevée pour que la pièce extrudée avant le soufflage ne se déforme pas ou faiblement sous l'effet de son propre poids. Toutefois, les propriétés mécaniques, élastiques et de résistance aux chocs des pièces ne doivent pas être affectées ou faiblement. Certaines solutions ont été proposées telles que l'utilisation de polyamides linéaires de haute viscosité obtenus par postcondensation en milieu solide, ou par addition d'agents d'extension de chaînes. Toutefois, ces solutions sont souvent difficiles à mettre en oeuvre ou altèrent certaines propriétés des pièces obtenues. The present invention relates to a high viscosity polyamide composition comprising a branched polyamide. It relates more particularly to a composition comprising a random tree type copolyamide resulting from the reaction between a multifunctional monomer comprising at least three reactive functions to form an amide function, these functions being of two different types, and bifunctional monomers conventionally used in the manufacture linear polyamides. The copolyamide obtained has a very low melt flow index relative to the linear polyamide and improved impact properties. The invention also relates to the use of this composition for the extrusion blow molding of articles. In the field of parts made of plastic, many parts are obtained by molding a composition comprising as matrix a polyamide. The polyamides generally used are linear aliphatic, aromatic or semi-aromatic polyamides. The new processes for shaping these compositions, such as, for example, extrusion blow molding, require compositions having a high melt viscosity so that the extruded part before blowing does not deform or weakly under the effect of its extrusion. own weight. However, the mechanical, elastic and impact properties of the parts must not be affected or weakly affected. Some solutions have been proposed such as the use of linear polyamides of high viscosity obtained by postcondensation in solid medium, or by addition of chain extension agents. However, these solutions are often difficult to implement or alter certain properties of the parts obtained.
L'invention a pour but un nouveau polyamide présentant une viscosité élevée en milieu fondu, qui peut être obtenu par un procédé de fabrication simple et contrôlable et avec des caractéristiques mécaniques satisfaisantes, sans pénaliser les différentes propriétés d'usage des articles fabriqués, tels que notamment la perméabilité. The object of the invention is a new polyamide having a high melt viscosity, which can be obtained by a simple and controllable manufacturing process and with satisfactory mechanical characteristics, without penalize the different properties of use of manufactured articles, such as in particular the permeability.
A cet effet, la présente invention invention propose une composition susceptible d'être obtenue par mélange d'au moins : a) un copolyamide de structure du type arbre statistique qui est le résultat de la réaction entre au moins : For this purpose, the present invention provides a composition obtainable by mixing at least: a) a random tree type structure copolyamide which is the result of the reaction between at least:
un monomère multifonctionnel répondant à la formule générale I suivante :  a multifunctional monomer having the following general formula I:
(AR1 )-R-(R2B)n (I) (AR 1 ) -R- (R 2 B) n (I)
dans laquelle : n est un nombre entier compris entre 2 et 10 (bornes incluses), Ri , R2 peuvent être identiques ou différents et représentent une liaison covalente, un radical hydrocarboné aliphatique, arylaliphatique, aromatique ou alkylaromatique, R est un radical aliphatique linéaire ou ramifié, un radical cycloaliphatique substitué ou non, un radical aromatique substitué ou non pouvant comprendre plusieurs noyaux aromatiques et/ou des hétérocétones, A représente la fonction amine ou sel d'amine, ou la fonction acide, ester, halogénure d'acide ou amide, B représente la fonction amine ou sel d'amine quand A représente une fonction acide, ester, halogénure d'acide ou amide, et une fonction acide, ester, halogénure d'acide ou amide quand A représente une fonction amine ou sel d'amine, au moins un des monomères bifonctionnels de formules II à IV suivantes : in which: n is an integer from 2 to 10 (inclusive), R1, R2 may be the same or different and represent a covalent bond, an aliphatic, arylaliphatic, aromatic or alkylaromatic hydrocarbon radical, R is a linear aliphatic radical or branched, a substituted or unsubstituted cycloaliphatic radical, a substituted or unsubstituted aromatic radical which may comprise several aromatic nuclei and / or heteroketones, A represents the amine or amine salt function, or the acid, ester, acid halide or amide function , B represents the amine or amine salt function when A represents an acid, ester, acid halide or amide function, and an acid, ester, acid halide or amide function when A represents an amine or salt function. amine, at least one of the following bifunctional monomers of formulas II to IV:
A1 -R3-A1 (II)  A1-R3-A1 (II)
B1 -R4-B1 (III) et/ou  B1 -R4-B1 (III) and / or
A1 -R5-B1 ou les lactames correspondants (IV) avec éventuellement au moins un des monomères monofonctionnels de formule V ou VI suivantes :  A1 -R5-B1 or the corresponding lactams (IV) with optionally at least one of the following monofunctional monomers of formula V or VI:
R6-B1 (V), et/ou  R6-B1 (V), and / or
R7-A1 (VI)  R7-A1 (VI)
dans lesquelles : Ai , B1 représentent respectivement une fonction acide, ester ou chlorure d'acide, et une fonction amine, ou un sel d'amine, R3, R4, R5, RQ, RJ représentent des radicaux hydrocarbonés alkyles linéaires ou ramifiés, aromatiques substitués ou non alkylaryles, arylalkyles ou cycloaliphatiques pouvant comprendre des insaturations ; et b) un extenseur de chaîne. in which: Ai, B1 respectively represent an acid, ester or acid chloride function, and an amine function, or an amine salt, R3, R4, R5, RQ, RJ represent linear or branched alkyl hydrocarbon radicals, substituted aromatic or non-alkylaryl, arylalkyl or cycloaliphatic radicals which may comprise unsaturations; and b) a chain extender.
Un tel copolyamide de structure du type arbre statistique est notamment décrit dans la demande WO99/03909. Selon une caractéristique préférentielle de l'invention, le radical R est un radical aromatique, R<| , R2 représentant chacun une liaison covalente. Par ailleurs, les fonctions B et A de la formule (I) sont respectivement une fonction acide et une fonction aminé, le nombre n de fonction acide étant avantageusement égal à 2. Ainsi, les monomères polyfonctionnels convenables et préférés de l'invention sont, notamment, les monomères stables thermiquement à une température supérieure à 150°C. A titre d'exemple, on peut citer les monomères polyfonctionnels conformes à la formule (I) dans laquelle R représente un radical aromatique tel que l'acide aminophtalique, ou un radical aliphatique linéaire tel que le diacide 3-aminopimélique, ou l'acide 6-amino undécandioïque. On peut également citer les α-aminoacides tels que l'acide aspartique, l'acide glutamique. Les aminoacides naturels peuvent également être utilisés comme monomère polyfonctionnel si leur stabilité thermique est suffisante. Les monomères difonctionnels de formules (II) à (IV) sont les monomères utilisés pour la fabrication de polyamide thermoplastique linéaires. Ainsi, on peut citer les composés ω-aminoalcanoïque comportant une chaîne hydrocarbonée ayant de 4 à 12 atomes de carbone, ou les lactames dérivés de ces acides aminoacides comme Γε-caprolactame, les diacides carboxyliques aliphatiques saturés ayant de 6 à 12 atomes de carbone tels que, par exemple l'acide adipique, acide azélaïque, acide sébacique, acide dodécanoïque, les diamines biprimaires de préférence aliphatiques saturées linéaires ou ramifiées ayant de 6 à 12 atomes de carbone telles que, par exemple, l'hexaméthylène diamine, la triméthylhexaméthylène diamine, la tétraméthylène diamine, la m-xylène diamine. Such a copolyamide structure of the statistical tree type is described in particular in the application WO99 / 03909. According to a preferred feature of the invention, the radical R is an aromatic radical, R <| , R2 each representing a covalent bond. Moreover, the functions B and A of the formula (I) are respectively an acid function and an amine function, the number n of acid function being advantageously equal to 2. Thus, the preferred and preferred polyfunctional monomers of the invention are, in particular, the thermally stable monomers at a temperature above 150 ° C. By way of example, mention may be made of polyfunctional monomers according to formula (I) in which R represents an aromatic radical such as aminophthalic acid, or a linear aliphatic radical such as 3-aminopimelic diacid, or the acid 6-amino undecandioic acid Mention may also be made of α-amino acids such as aspartic acid or glutamic acid. Natural amino acids can also be used as a polyfunctional monomer if their thermal stability is sufficient. The difunctional monomers of formulas (II) to (IV) are the monomers used for the manufacture of linear thermoplastic polyamide. Thus, mention may be made of the ω-aminoalkanoic compounds comprising a hydrocarbon chain containing from 4 to 12 carbon atoms, or the lactams derived from these amino acid acids such as ε-caprolactam, the saturated aliphatic carboxylic diacids containing from 6 to 12 carbon atoms such as that, for example, adipic acid, azelaic acid, sebacic acid, dodecanoic acid, preferably linear or branched saturated aliphatic biprimary diamines having from 6 to 12 atoms carbon such as, for example, hexamethylenediamine, trimethylhexamethylenediamine, tetramethylenediamine, m-xylene diamine.
Bien entendu, des mélanges de ces monomères peuvent être utilisés. Of course, mixtures of these monomers may be used.
Les monomères bifonctionnels préférés de l'invention sont Γε-caprolactame, ou l'hexaméthylène diamine et l'acide adipique ou un mélange de ceux-ci. The preferred bifunctional monomers of the invention are ε-caprolactam, or hexamethylenediamine and adipic acid or a mixture thereof.
Le rapport molaire entre les monomères multifonctionnels de formule (I) et la somme des monomères bifonctionnels de formules (II) à (IV) et monomères monofonctionnels de formules (V) et (VI) est préférentiellement compris entre 0,01 % et 5 %, de préférence entre 0,05 % et 1 % pour obtenir un copolyamide présentant un niveau de propriétés mécaniques équivalent à celui du polyamide linéaire correspondant. The molar ratio between the multifunctional monomers of formula (I) and the sum of the bifunctional monomers of formulas (II) to (IV) and monofunctional monomers of formulas (V) and (VI) is preferably between 0.01% and 5% preferably between 0.05% and 1% to obtain a copolyamide having a level of mechanical properties equivalent to that of the corresponding linear polyamide.
Le copolyamide présente de préférence un indice de fluidité en milieu fondu (M.F.I.) inférieur à 5 g/10 min (mesuré à 275°C sous une charge de 2160 g), et avantageusement un indice de distribution D des masses moléculaires supérieur à 2. L'indice de distribution D des masses moléculaires est une fonction du degré de polymérisation DPn et du facteur de fonctionnalité F du polymère. The copolyamide preferably has a melt flow index (MFI) of less than 5 g / 10 min (measured at 275 ° C under a load of 2160 g), and preferably a molecular weight distribution index D of greater than 2. The distribution index D of the molecular masses is a function of the degree of polymerization DPn and the factor of functionality F of the polymer.
La polymérisation est notamment réalisée selon les conditions opératoires classiques de polymérisation des diacides carboxyliques et diamines, quand celle- ci est réalisée en absence des composés multifonctionnels. The polymerization is in particular carried out according to the conventional operating conditions of polymerization of dicarboxylic acids and diamines, when this is carried out in the absence of multifunctional compounds.
Un tel procédé de polymérisation peut comprendre brièvement : Such a polymerization process may briefly include:
un chauffage sous agitation et sous pression du mélange des monomères et composés multifonctionnels,  heating under stirring and under pressure the mixture of monomers and multifunctional compounds,
un maintien du mélange sous pression et température pendant une durée déterminée, avec élimination de vapeur d'eau par un dispositif approprié, puis décompression et maintien pendant une durée déterminée à une température supérieure au point de fusion du mélange, notamment sous pression autogène de vapeur d'eau, sous azote ou sous vide, pour ainsi continuer la polymérisation par élimination de l'eau formée. maintaining the mixture under pressure and temperature for a predetermined period, with the removal of steam by a suitable device, then decompression and maintaining for a predetermined time at a temperature above the melting point of the mixture, in particular under autogenous pressure of water vapor, under nitrogen or under vacuum, to thereby continue the polymerization by removing the water formed.
On peut parfaitement conduire la polymérisation jusqu'à l'obtention de l'équilibre thermodynamique du polyamide. The polymerization can be perfectly carried out until the thermodynamic equilibrium of the polyamide is obtained.
Les composés multifonctionnels et éventuellement monofonctionnels sont préférentiellement ajoutés au début de la polymérisation. Dans ce cas on procède à la polymérisation d'un mélange des monomères diacides carboxyliques et diamines et des composés multifonctionnels et monofonctionnels. The multifunctional and optionally monofunctional compounds are preferably added at the beginning of the polymerization. In this case, the polymerization of a mixture of dicarboxylic and diamine monomers and multifunctional and monofunctional compounds is carried out.
On peut parfaitement ajouter en début, en cours ou en fin de polymérisation des additifs usuels, tels que par exemple des catalyseurs, comme notamment des catalyseurs phosphorés, des agents anti-mousse, et des agents stabilisants à la lumière ou la chaleur. It is perfectly possible to add, at the beginning, during or at the end of the polymerization, usual additives, such as, for example, catalysts, such as, in particular, phosphorus catalysts, antifoam agents, and agents that stabilize light or heat.
En sortie de polymérisation, le polymère peut être refroidi avantageusement par de l'eau, et extrudé, puis coupé pour produire des granulés. Le procédé de polymérisation selon l'invention peut parfaitement être réalisé en continu ou en discontinu. At the polymerization outlet, the polymer can be cooled advantageously with water, and extruded and cut to produce granules. The polymerization process according to the invention can perfectly be carried out continuously or discontinuously.
Les extenseurs de chaîne du polyamide sont habituellement capable de réagir avec les groupements terminaux du polyamide aminés ou acides. Les extenseurs de chaînes présentent au moins deux fonctions capables de réagir avec les groupement terminaux du polyamide de manière a connecter deux chaînes polyamides et ainsi accroître la viscosité du polyamide modifié. L'utilisation de bis- lactames est notamment mentionné dans le brevet US 2,682,526. On peut notamment citer comme extendeurs de chaîne selon l'invention sont composés choisis dans le groupe constitué par : les dialcools tels que l'éthylène glycol, le propane diol, le butane diol, l'hexane diol, l'hydroquinone-bis- hydroxyéthyl éther, les bis époxydes tel que le diglicydyl éther de bisphénol A, les polymères portant des fonctions epoxyde, les polymères portant des fonctions anhydride, les bis-N-acyl bis-caprolactames, tels que l'isophthaloyl bis- caprolactame (IBC), l'adipoyle bis-caprolactame (ABC), le terphthaloyl bis- caprolactame (TBC), les diphényle carbonates, les bisoxazolines, les oxazolinones, les diisocyanates, les phosphites organiques, tel que tri phényle phosphite, caprolactame phosphite, bis ketenimines, dianhydrides. The chain extenders of the polyamide are usually capable of reacting with the end groups of the amino or acidic polyamide. The chain extenders have at least two functions capable of reacting with the end groups of the polyamide so as to connect two polyamide chains and thus increase the viscosity of the modified polyamide. The use of bis-lactams is especially mentioned in US Pat. No. 2,682,526. As chain extenders according to the invention, mention may especially be made of compounds chosen from the group consisting of: dialcohols such as ethylene glycol, propane diol, butane diol, hexane diol, hydroquinone-bis-hydroxyethyl ether, bis epoxides such as diglicydyl ether of bisphenol A, Polymers carrying epoxide functions, polymers bearing anhydride functions, bis-N-acyl bis-caprolactams, such as isophthaloyl bis-caprolactam (IBC), adipoyl bis-caprolactam (ABC), terphthaloyl bis-caprolactam (TBC), diphenyl carbonates, bisoxazolines, oxazolinones, diisocyanates, organic phosphites, such as tri phenyl phosphite, caprolactam phosphite, bis ketenimines, dianhydrides.
La composition comprend préférentiellement de 0,01 à 5 % en poids d'extenseurs de chaîne du polyamide, par rapport au poids total de la composition. Plus préférentiellement la composition comprend de 0,1 à 3 % en poids d'extenseurs de chaîne du polyamide, par rapport au poids total de la composition. On peut notamment utiliser de 0,01 à 10 % en poids d'extenseurs de chaîne du polyamide, par rapport au poids du polyamide. Les chaînes extendeurs préférrés sont insensibles à la teneur en humidité du polyamide dans les conditions de la réaction de polyamidation, et ne génère pas de produits secondaires. The composition preferably comprises from 0.01 to 5% by weight of chain extenders of the polyamide, relative to the total weight of the composition. More preferentially, the composition comprises from 0.1 to 3% by weight of chain extenders of the polyamide, relative to the total weight of the composition. In particular, 0.01 to 10% by weight of chain extenders of the polyamide may be used, relative to the weight of the polyamide. Preferred extender chains are insensitive to the moisture content of the polyamide under the conditions of the polyamidation reaction, and do not generate byproducts.
Pour améliorer les propriétés mécaniques de cette composition, il peut être avantageux de lui adjoindre au moins une charge de renfort et/ou de remplissage préférentiellement choisie dans le groupe comprenant les charges fibreuses telles que les fibres de verre, les charges minérales telles que les argiles, le kaolin, ou des nanoparticules renforçantes ou en matière thermo-durcissable, et les charges en poudre telles que le talc. Le taux d'incorporation en charge de renfort et/ou de remplissage est conforme aux standards dans le domaine des matériaux composites. Il peut s'agir par exemple d'un taux de charge de 1 à 80 %, de préférence de 10 à 70 %, notamment entre 30 et 60 %. To improve the mechanical properties of this composition, it may be advantageous to add at least one reinforcing and / or filling filler preferentially chosen from the group comprising fibrous fillers such as glass fibers, mineral fillers such as clays. , kaolin, or reinforcing nanoparticles or thermo-hardenable material, and powder fillers such as talc. The rate of incorporation in reinforcing and / or filling load is in accordance with the standards in the field of composite materials. It may be for example a charge rate of 1 to 80%, preferably 10 to 70%, especially between 30 and 60%.
La composition peut comprendre, outre le polyamide modifié de l'invention, un ou plusieurs autres polymères, de préférence polyamides ou copolyamides. The composition may comprise, in addition to the modified polyamide of the invention, one or more other polymers, preferably polyamides or copolyamides.
La composition selon l'invention peut en outre comprendre des additifs usuellement utilisés pour la fabrication de compositions polyamides destinées à être moulées. Ainsi, on peut citer les lubrifiants, les agents ignifugeants, les plastifiants, les agents nucléants, les catalyseurs, les agents d'amélioration de la résilience comme des élastomères éventuellement greffés, les stabilisants lumière et/ou thermique, les antioxydants, les antistatiques, les colorants, les matifiants, les additifs d'aide au moulage ou autres additifs conventionnels. The composition according to the invention may further comprise additives usually used for the manufacture of polyamide compositions for to be molded. Thus, mention may be made of lubricants, flame-retardants, plasticizers, nucleating agents, catalysts, resilience-improving agents such as optionally grafted elastomers, light and / or thermal stabilizers, antioxidants, antistats, dyes, matifying agents, molding aid additives or other conventional additives.
Ces charges et additifs peuvent être ajoutés au polyamide modifié par des moyens usuels adaptés à chaque charge ou additif, tel que par exemple lors de la polymérisation ou en mélange à froid ou en fondu. These fillers and additives may be added to the modified polyamide by conventional means suitable for each filler or additive, such as for example during the polymerization or in cold or melt blending.
La composition selon l'invention comprenant le polyamide tel que défini précédemment peut également comprendre au moins un agent modificateur du choc, c'est-à-dire un composé capable de modifier la résistance aux chocs d'une composition polyamide. Ces composés modificateurs du choc comprennent préférentiellement des groupements fonctionnels réactifs avec le polyamide. The composition according to the invention comprising the polyamide as defined above may also comprise at least one impact modifier, that is to say a compound capable of modifying the impact resistance of a polyamide composition. These shock-modifying compounds preferably comprise functional groups that are reactive with the polyamide.
On entend selon l'invention par groupements fonctionnels réactifs avec le polyamide, des groupements capables de réagir ou d'interagir chimiquement avec les fonctions acides ou aminés du polyamide, notamment par covalence, interaction ionique ou hydrogène ou liaison de van der Walls. De tels groupements réactifs permettent d'assurer une bonne dispersion des agents modificateurs de chocs dans la matrice polyamide. On obtient généralement une bonne dispersion avec des particules d'agents modificateurs de chocs ayant une taille moyenne comprise entre 0,1 et 1 μιτι dans la matrice. The term "polyamide-reactive functional groups" according to the invention is understood to mean groups capable of reacting or chemically interacting with the acidic or amine functional groups of the polyamide, in particular by covalence, ionic interaction or hydrogen or van der Walls bonding. Such reactive groups make it possible to ensure good dispersion of the impact modifiers in the polyamide matrix. Good dispersion is generally obtained with particles of impact modifying agents having an average size of between 0.1 and 1 μιτι in the matrix.
On utilise préférentiellement des agents modificateur du choc comprenant des groupements fonctionnels réactifs avec le polyamide en fonction de la nature acide ou amine du ΔΘΤ du polyamide. Ainsi par exemple, si le ΔΘΤ est acide on utilisera préférentiellement des groupements fonctionnels réactifs capables de réagir ou d'interagir chimiquement avec les fonctions acides du polyamide, notamment par covalence, interaction ionique ou hydrogène ou liaison de van der Walls. Si par exemple, si le ΔΘΤ est amine on utilisera préférentiellement des groupements fonctionnels réactifs capables de réagir ou d'interagir chimiquement avec les fonctions aminés du polyamide, notamment par covalence, interaction ionique ou hydrogène ou liaison de van der Walls. Shock modifiers comprising functional groups reactive with the polyamide are preferably used depending on the acid or amine nature of the ΔΘΤ of the polyamide. Thus, for example, if the ΔΘΤ is acidic, it will be preferable to use reactive functional groups capable of reacting or chemically interacting with the acid functions of the polyamide, in particular by covalence, ionic interaction or hydrogen or van der Walls bonding. If, for example, if the ΔΘΤ is amine, it will be preferable to use reactive functional groups capable of reacting or chemically interacting with the amine functions of the polyamide, in particular by covalence, ionic interaction or hydrogen or van der Walls bonding.
On utilise préférentiellement des agents modificateurs du choc ayant des groupements fonctionnels réactifs avec le polyamide présentant un ΔΘΤ de nature aminé. Shock modifiers having functional groups reactive with the polyamide having an ΔΘΤ of amine nature are preferably used.
Les agents modificateurs du choc peuvent très bien comprendre en eux-mêmes des groupements fonctionnels réactifs avec le polyamide, par exemple pour ce qui concerne l'éthylènes acide acrylique (EAA). The shock-modifying agents can very well comprise functional groups reactive with the polyamide, for example with regard to acrylic acid ethylenes (EAA).
Il est également possible de leur adjoindre des groupements fonctionnels réactifs avec le polyamide, généralement par greffage ou copolymérisation, par exemple pour l'éthylène-propylène-diène (EPDM) greffé par de l'anhydride maléique. It is also possible to add functional groups reactive with the polyamide, generally by grafting or copolymerization, for example for ethylene-propylene-diene (EPDM) grafted with maleic anhydride.
On peut utiliser selon l'invention, les agents modificateurs de chocs qui sont des composés, oligomériques ou polymériques, comprenant au moins un des monomères suivants, ou leur mélange : éthylène, propylène, butène, isoprène, diène, acrylate, butadiène, styrène, octène, acrylonitrile, acide acrylique, acide méthacrylique, vinyle acétate, esters vinyliques tels que les esters acryliques et méthacryliques et le glycidile méthacrylate. Ces composés selon l'invention peuvent également comprendre en plus d'autres monomères que ceux mentionnés précédemment. La base du composé modificateur du choc, éventuellement appelé base élastomérique, peut être choisie dans le groupe comprenant : les polyéthylènes, les polypropylènes, les polybutènes, les polyisoprènes, les caoutchoucs d'éthylène-propylène (EPR), les caoutchoucs d'éthylène-propylène-diène (EPDM), les caoutchoucs d'éthylène et de butène, les caoutchoucs d'éthylène et d'acrylate, les caoutchoucs de butadiène et de styrène, les caoutchoucs de butadiène et d'acrylate, les caoutchoucs d'éthylène et octène, les caoutchoucs butadiène acrylonitrile, les éthylène acide acrylique (EAA), les éthylène vinyle acétate (EVA), les éthylène ester acrylique (EEA), les copolymères acrylonitrile butadiène styrène (ABS), les copolymères block styrène éthylène butadiène styrène (SEBS), les copolymères styrène butadiène styrène (SBS), les élastomères core-shell type méthacrylate-butadiène-styrène (MBS), ou des mélanges d'au moins deux élastomères listés ci-dessus. According to the invention, the impact modifying agents which are compounds, oligomeric or polymeric, comprising at least one of the following monomers, or their mixture: ethylene, propylene, butene, isoprene, diene, acrylate, butadiene, styrene, octene, acrylonitrile, acrylic acid, methacrylic acid, vinyl acetate, vinyl esters such as acrylic and methacrylic esters and glycidyl methacrylate. These compounds according to the invention may also comprise in addition to other monomers than those mentioned above. The base of the impact-modifying compound, optionally called the elastomeric base, can be chosen from the group comprising: polyethylenes, polypropylenes, polybutenes, polyisoprenes, ethylene-propylene rubbers (EPR), ethylene-rubbers, propylene-diene (EPDM), ethylene and butene rubbers, ethylene and acrylate rubbers, butadiene and styrene rubbers, butadiene and acrylate rubbers, ethylene and octene rubbers , butadiene acrylonitrile rubbers, ethylene acrylic acid (EAA), ethylene vinyl acetate (EVA), ethylene acrylic ester (EEA), acrylonitrile copolymers butadiene styrene (ABS), styrene ethylene butadiene styrene block copolymers (SEBS), styrene butadiene styrene copolymers (SBS), core-shell methacrylate-butadiene-styrene (MBS) elastomers, or mixtures of two or more elastomers listed above.
En plus des groupements listés ci-dessus, ces agent modificateurs de chocs peuvent comprendre également, généralement greffés ou copolymérisés, des groupements fonctionnels réactifs avec le polyamide, tel que notamment des groupements fonctionnels suivant : les acides, tels que les acides carboxyliques, les acides salifiés, les esters en particulier, les acrylates et les méthacrylates, les ionomères, les groupes glycidyls notamment époxy, les esters glycidyls, les anhydrides notamment les anhydrides maléiques, les oxazolines, les maléïmides, ou leurs mélanges. Des tels groupements fonctionnels sur les élastomères sont par exemple obtenus par utilisation d'un co-monomère lors de la préparation de l'élastomère. In addition to the groups listed above, these shock-modifying agents can also comprise, generally grafted or copolymerized, functional groups that are reactive with the polyamide, such as in particular the following functional groups: acids, such as carboxylic acids, acids salified esters in particular, acrylates and methacrylates, ionomers, glycidyl groups including epoxy, glycidyl esters, anhydrides including maleic anhydrides, oxazolines, maleimides, or mixtures thereof. Such functional groups on the elastomers are for example obtained by using a comonomer during the preparation of the elastomer.
Comme agents modificateurs de chocs comprenant des groupements fonctionnels réactifs avec le polyamide, on peut notamment citer les terpolymères d'éthylène, ester acrylique et glycidyl méthacrylate, les copolymères d'éthylène et de butyl ester acrylate, les copolymères d'éthylène, n-butyl acrylate et glycidyl méthacrylate, les copolymères d'éthylène et d'anhydride maléique, les copolymères styrène-maléïmides greffés avec de l'anhydride maléique, les copolymères styrène-éthylène-butylène-styrène modifié avec de l'anhydride maléique, les copolymère styrène-acrylonitrile greffés anhydrides maléiques, les copolymères acrylonitrile butadiène styrène greffés anhydrides maléiques, et leurs versions hydrogénées. As impact-modifying agents comprising functional groups that are reactive with the polyamide, there may be mentioned terpolymers of ethylene, acrylic ester and glycidyl methacrylate, copolymers of ethylene and butyl ester acrylate, copolymers of ethylene, n-butyl acrylate and glycidyl methacrylate, copolymers of ethylene and maleic anhydride, styrene-maleimide copolymers grafted with maleic anhydride, styrene-ethylene-butylene-styrene copolymers modified with maleic anhydride, styrene-maleic anhydride copolymers, acrylonitrile grafted maleic anhydrides, acrylonitrile butadiene styrene copolymers grafted maleic anhydrides, and their hydrogenated versions.
La proportion en poids des agents modificateur du choc dans la composition totale est notamment comprise entre 0,1 et 50 %, préférentiellement entre 0,1 et 20 %, notamment entre 0,1 et 10 %, par rapport au poids total de la composition. La composition selon la présente invention comprend tout préfentiellement un copolyamide de structure du type arbre statistique, un extenseur de chaîne et un agent modificateur de chocs. Selon une caractéristique de l'invention, les compositions de l'invention sont obtenues par mélange généralement dans une extrudeuse mono ou bivis, d'un polyamide conforme à l'invention avec les différents additifs, ce mélange étant réalisé généralement à l'état fondu du polyamide, puis extrusion du mélange sous forme de joncs qui sont ensuite découpés en granulés. Les pièces moulées sont ensuite réalisées par fusion des granulés produits ci-dessus et alimentation de la composition à l'état fondu dans les dispositifs de moulage, d'injection ou d'extrusion appropriés. The proportion by weight of the impact-modifying agents in the total composition is in particular between 0.1 and 50%, preferably between 0.1 and 20%, especially between 0.1 and 10%, relative to the total weight of the composition. . The composition according to the present invention preferably comprises a random tree structure copolyamide, a chain extender and a shock modifier. According to one characteristic of the invention, the compositions of the invention are obtained by generally mixing in a single or twin-screw extruder, a polyamide according to the invention with the various additives, this mixture being generally carried out in the molten state. polyamide, then extrusion of the mixture in the form of rods which are then cut into granules. The molded parts are then made by melting the granules produced above and supplying the composition in the molten state into the appropriate molding, injection or extrusion devices.
La composition selon l'invention peut être utilisés dans de nombreuses applications telles que la fabrication de pièces moulées ou injectées ou soufflés. La composition est particulièrement convenable pour la fabrication de pièces par les techniques d'extrusion-soufflage en continu ou discontinu, avec ou sans tête d'accumulation. En effet, la faible fluidité en milieu fondu de la composition permet de limiter les déformations des paraisons lors de leur extrusion, avant l'étape de soufflage. La présente invention concerne également un procédé de soufflage par extrusion mettant en œuvre une composition polyamide selon l'invention. The composition according to the invention can be used in many applications such as the manufacture of molded or injected or blown parts. The composition is particularly suitable for the manufacture of parts by continuous or discontinuous extrusion blow molding techniques, with or without an accumulation head. Indeed, the low melt fluidity of the composition makes it possible to limit the deformations of the parisons during their extrusion, before the blowing step. The present invention also relates to an extrusion blow molding process using a polyamide composition according to the invention.
La composition selon l'invention peut également aussi être utilisée comme matrice dans une composition comprenant une forte proportion d'additifs de type mélange maître (masterbatch) destinée à être mélangée à une autre composition thermoplastique. Les compositions de l'invention peuvent également comprendre comme matrice polymérique, en plus du polyamide tel que décrit ci-dessus, d'autres matières thermoplastiques telles que des polyamides linéaires aliphatiques ou des polyamides aromatiques ou semi-aromatiques, par exemple. The composition according to the invention can also also be used as a matrix in a composition comprising a high proportion of masterbatch additives intended to be mixed with another thermoplastic composition. The compositions of the invention may also comprise, as polymeric matrix, in addition to the polyamide as described above, other thermoplastic materials such as linear aliphatic polyamides or aromatic or semi-aromatic polyamides, for example.
Des termes spécifiques sont utilisés dans la description de manière à faciliter la compréhension du principe de l'invention. Il doit néanmoins être compris qu'aucune limitation de la portée de l'invention n'est envisagée par l'utilisation de ces termes spécifiques. Le terme et/ou inclut les significations et, ou, ainsi que toutes les autres combinaisons possibles des éléments connectés à ce terme. Specific terms are used in the description to facilitate understanding of the principle of the invention. It must be understood, however, that no limitation of the scope of the invention is envisaged by the use of these specific terms. The term and / or includes the meanings and, or, as well as all other possible combinations of elements connected to this term.
D'autres détails ou avantages de l'invention apparaîtront plus clairement au des exemples ci-dessous, donnés uniquement à titre indicatif. Other details or advantages of the invention will appear more clearly in the examples below, given solely for information purposes.
PARTIE EXPERIMENTALE EXPERIMENTAL PART
Les composés utilisés sont les suivants :  The compounds used are the following:
Polyamide a) de type arbre statistique obtenu selon la demande WO99/03909 en utilisant 0,185 % molaire d'acide amino-5 isophtalique et 99,8 % d's-caprolactame. Le polyamide présente un indice de fluidité en milieu fondu (MFI) de 5 à 10 g/10 min (selon la norme ASTM D1238 sous une charge de 2160 g et à une température de 275°C) ; et un index de viscosité 200 à 225 ml/g (déterminé dans l'acide formique selon la méthode PN-EN ISO 307)  Polyamide a) of random tree type obtained according to the application WO99 / 03909 using 0.185 mol% of 5-isophthalic acid and 99.8% of ε-caprolactam. The polyamide has a melt flow index (MFI) of 5 to 10 g / 10 min (according to ASTM D1238 under a load of 2160 g and at a temperature of 275 ° C); and a viscosity index of 200 to 225 ml / g (determined in formic acid according to the method PN-EN ISO 307)
- Polyamide 66 linaire ayant un IV de 175 ml/g (déterminé dans l'acide formique à 90% selon la norme ISO 307) Linear polyamide 66 having an IV of 175 ml / g (determined in 90% formic acid according to ISO 307)
extenseur de chaîne : Araldite GT7071 , SMA Xiran XZ-09-002 (Polyscope) (copolymere du styrène avec anhydride maleique))  chain extender: Araldite GT7071, SMA Xiran XZ-09-002 (Polyscope) (copolymer of styrene with maleic anhydride))
modificateur de chocs : Exxelor VA1801 (copolymère éthylènique greffé anhydride maléique)  impact modifier: Exxelor VA1801 (maleic anhydride grafted ethylenic copolymer)
Des formulations polyamides sont fabriquées par mélange à l'état fondu en extrudeuse bi-vis type Werner et Pfleiderer ZSK 40 avec dégazage (L/D=36), du polyamide a), avec diverses proportions en poids d'extenseur de chaîne, 25 % en poids de modificateurs de chocs et 2 % en poids de stabilisant. Les paramètres d'extrusion sont les suivants : température d'extrusion avec un profil croissant 250-270°C ; vitesse de rotation de la vis : 250 tours par minute ; débit de la composition 40 kg/h ; le couple moteur et la puissance moteur absorbée varient selon les polyamides. Tableau 1 Polyamide formulations are made by melt blending in a Werner and Pfleiderer ZSK 40 twin-screw extruder with degassing (L / D = 36), polyamide a), with various weight proportions of chain extender, % by weight of impact modifiers and 2% by weight of stabilizer. The extrusion parameters are as follows: extrusion temperature with increasing profile 250-270 ° C; speed of rotation of the screw: 250 rpm; flow rate of the composition 40 kg / h; the engine torque and the engine power absorbed vary depending on the polyamides. Table 1
Différentes propriétés mécaniques ont été mesurées sur ces formulations et les résultats sont mentionnés dans le tableau suivant.  Different mechanical properties were measured on these formulations and the results are mentioned in the following table.
Tableau 2 Table 2
nm = non mesuré nm = not measured
Le choc Charpy entaillé est mesuré selon la norme ISO 179-1/1 eA. La viscosité est mesurée à l'aide d'un rhéomètre capillaire Gôttfert 2002. Un piston se déplaçant à vitesses programmées pousse le polymère fondu à travers un capillaire de longueur L (30 mm) et de diamètre D (1 mm). Le débit correspondant est mesuré duquel on peut déduire la viscosité apparente. Un balayage en gradient de cisaillement est effectué de 5000 s"1 à 10s"1. The notched Charpy impact is measured according to ISO 179-1 / 1 eA. The viscosity is measured using a Gottfert capillary rheometer 2002. A piston moving at programmed speeds pushes the molten polymer through a capillary of length L (30 mm) and diameter D (1 mm). The corresponding flow rate is measured from which the apparent viscosity can be deduced. A shear rate sweep is performed from 5000 s -1 to 10 s -1 .
Le melt strenght est mesuré de la manière suivante : on introduit le polymère formulé dans une machine de soufflage mono vis à un profile de température de 250-275°C et à une vitesse de visse fixés de 40 tour par minute ; et on enregistre à l'aide de photocellules le temps nécessaire pour permettre au paraison de polymère fondu de parcourir une distance de 75 cm. La mesure est répétée au moins 5 fois afin de vérifier la faible déviation standard. Ainsi, plus le temps de parcourt est grand et plus le polymère présente une tenue morphologique avantageuse pour la fabrication d'articles par extrusion soufflage. The melt strenght is measured in the following manner: the polymer formulated in a single screw blowing machine is introduced at a temperature profile of 250-275 ° C. and at a fixed screw speed of 40 rpm; and the time required to allow the parison of molten polymer to travel a distance of 75 cm is recorded with the aid of photocells. The measurement is repeated at least 5 times in order to check the standard low deviation. Thus, the longer the running time is large and more the polymer has a morphological strength advantageous for the manufacture of articles by extrusion blow molding.
On observe ainsi que l'ajout d'un agent extenseur de chaîne en combinaison avec le polyamide de l'invention permet d'augmenter significativement la qualité de la paraison extrudé. On observe par ailleurs que dans le cadre de la combinaison selon l'invention une augmentation de 19 % environ de la viscosité apparente à un gradient de cisaillement de 10 s"1 (comparaison de l'exemple 3 avec C1 ). A contrario, le simple ajout d'un agent extenseur de chaîne à un polyamide 66 linéaire comme classiquement effectué dans l'art antérieur conduit à une augmentation de 4 % environ de cette viscosité apparente (comparaison C3 ou C4 avec C2). Cette haute viscosité rend d'autant plus aisé la fabrication d'articles par soufflage par extrusion ainsi que la qualité de l'article obtenu. It is thus observed that the addition of a chain extender in combination with the polyamide of the invention makes it possible to significantly increase the quality of the extruded parison. It is furthermore observed that in the context of the combination according to the invention an increase of about 19% in the apparent viscosity at a shear rate of 10 s -1 (comparison of Example 3 with Cl). simple addition of a chain extender agent to a linear polyamide 66 as conventionally carried out in the prior art leads to an increase of about 4% in this apparent viscosity (C3 or C4 comparison with C2) .This high viscosity easier to manufacture articles by extrusion blow molding as well as the quality of the article obtained.

Claims

REVENDICATIONS
1 . Composition susceptible d'être obtenue par mélange d'au moins : a) un copolyamide de structure du type arbre statistique qui est le résultat de la réaction entre au moins : 1. A composition obtainable by mixing at least: a) a random tree type structure copolyamide which is the result of the reaction between at least:
un monomère multifonctionnel répondant à la formule générale I suivante :  a multifunctional monomer having the following general formula I:
(AR1 )-R-(R2B)n (I) (AR 1 ) -R- (R 2 B) n (I)
dans laquelle : n est un nombre entier compris entre 2 et 10 (bornes incluses), Ri , R2 peuvent être identiques ou différents et représentent une liaison covalente, un radical hydrocarboné aliphatique, arylaliphatique, aromatique ou alkylaromatique, R est un radical aliphatique linéaire ou ramifié, un radical cycloaliphatique substitué ou non, un radical aromatique substitué ou non pouvant comprendre plusieurs noyaux aromatiques et/ou des hétérocétones, A représente la fonction amine ou sel d'amine, ou la fonction acide, ester, halogénure d'acide ou amide, B représente la fonction amine ou sel d'amine quand A représente une fonction acide, ester, halogénure d'acide ou amide, et une fonction acide, ester, halogénure d'acide ou amide quand A représente une fonction amine ou sel d'amine, au moins un des monomères bifonctionnels de formules II à IV suivantes : in which: n is an integer from 2 to 10 (inclusive), R1, R2 may be the same or different and represent a covalent bond, an aliphatic, arylaliphatic, aromatic or alkylaromatic hydrocarbon radical, R is a linear aliphatic radical or branched, a substituted or unsubstituted cycloaliphatic radical, a substituted or unsubstituted aromatic radical which may comprise several aromatic nuclei and / or heteroketones, A represents the amine or amine salt function, or the acid, ester, acid halide or amide function , B represents the amine or amine salt function when A represents an acid, ester, acid halide or amide function, and an acid, ester, acid halide or amide function when A represents an amine or salt function. amine, at least one of the following bifunctional monomers of formulas II to IV:
A1 -R3-A1 (II)  A1-R3-A1 (II)
B-i -R^B-i (III) et/ou  B-i -R ^ B-i (III) and / or
A1 -R5-B1 ou les lactames correspondants (IV) avec éventuellement au moins un des monomères monofonctionnels de formule V ou VI suivantes :  A1 -R5-B1 or the corresponding lactams (IV) with optionally at least one of the following monofunctional monomers of formula V or VI:
R6-B (V), et/ou R 6 -B (V), and / or
R7-A1 (VI)  R7-A1 (VI)
dans lesquelles : Ai , B1 représentent respectivement une fonction acide, ester ou chlorure d'acide, et une fonction amine, ou un sel d'amine, R3, R4, R5, R6, R7 représentent des radicaux hydrocarbonés alkyles linéaires ou ramifiés, aromatiques substitués ou non alkylaryles, arylalkyles ou cycloaliphatiques pouvant comprendre des insaturations ; et b) un extenseur de chaîne. in which: Ai, B1 respectively represent an acid, ester or acid chloride function, and an amine function, or an amine salt, R3, R4, R5, R6, R7 represent linear or branched alkyl hydrocarbon radicals, substituted or non-alkylaryl, arylalkyl or cycloaliphatic aromatic compounds which may comprise unsaturations; and b) a chain extender.
2. Composition selon la revendication 1 , caractérisée en ce que le radical R est un radical aromatique. 2. Composition according to claim 1, characterized in that the radical R is an aromatic radical.
3. Composition selon l'une des revendications 1 à 2, caractérisée en ce que le monomère de formule (I) est un composé dans lequel A représente la fonction aminé, B la fonction acide, n est égal à 2 et R représente un radical aromatique, Ri et R2 représentent une liaison covalente. 3. Composition according to one of claims 1 to 2, characterized in that the monomer of formula (I) is a compound in which A represents the amine function, B the acid function, n is equal to 2 and R represents a radical aromatic, Ri and R2 represent a covalent bond.
4. Composition selon l'une des revendications 1 à 3, caractérisée en ce que le monomère de formule (I) est l'acide 5-amino-isophtalique. 4. Composition according to one of claims 1 to 3, characterized in that the monomer of formula (I) is 5-amino-isophthalic acid.
5. Composition selon la revendication 1 , caractérisée en ce que le monomère de formule (I) est l'acide 6-amino-undécandioïque. 5. Composition according to claim 1, characterized in that the monomer of formula (I) is 6-amino-undecandioic acid.
6. Composition selon l'une des revendications précédentes, caractérisée en ce que le copolyamide présente un indice de fluidité en milieu fondu inférieur à 5 g/10 min ; mesuré à 275°C sous une charge de 2160 g. 6. Composition according to one of the preceding claims, characterized in that the copolyamide has a melt flow index of less than 5 g / 10 min; measured at 275 ° C under a load of 2160 g.
7. Composition selon l'une des revendications précédentes, caractérisée en ce qu'il présente un indice de distribution D des masses moléculaires supérieur à 2. 7. Composition according to one of the preceding claims, characterized in that it has a molecular weight distribution index D greater than 2.
8. Composition selon l'une des revendications précédentes, caractérisée en ce que l'extendeur de chaîne est choisi dans le groupe constitué par : les dialcools tels que l'éthylène glycol, le propane diol, le butane diol, l'hexane diol, l'hydroquinone-bis-hydroxyéthyl éther, les bis époxydes tel que le diglicydyl éther de bisphénol A, les polymères portant des fonctions epoxyde, les polymères portant des fonctions anhydride, les bis-N-acyl bis-caprolactames, tels que l'isophthaloyl bis-caprolactame, l'adipoyle bis-caprolactame, le terphthaloyl bis- caprolactame, les diphényle carbonates, les bisoxazolines, les oxazolinones, les diisocyanates, les phosphites organiques, tel que tri phényle phosphite, caprolactame phosphite, bis ketenimines, dianhydrides. 8. Composition according to one of the preceding claims, characterized in that the chain extender is chosen from the group consisting of: dialcohols such as ethylene glycol, propane diol, butane diol, hexane diol, hydroquinone-bis-hydroxyethyl ether, bis epoxides such as bisphenol A diglicydyl ether, polymers carrying epoxide functions, polymers bearing anhydride functions, bis-N-acyl bis-caprolactams, such as isophthaloyl bis-caprolactam, adipoyl bis-caprolactam, terphthaloyl bis- caprolactam, diphenyl carbonates, bisoxazolines, oxazolinones, diisocyanates, organic phosphites, such as tri phenyl phosphite, caprolactam phosphite, bis ketenimines, dianhydrides.
9. Composition selon l'une des revendications précédentes, caractérisée en ce qu'elle comprend de 0,01 à 5 % en poids d'extenseurs de chaîne du polyamide, par rapport au poids total de la composition. 9. Composition according to one of the preceding claims, characterized in that it comprises from 0.01 to 5% by weight of chain extender polyamide, relative to the total weight of the composition.
10. Composition selon l'une des revendications précédentes, caractérisée qu'elle comprend un agent modificateur du choc. 10. Composition according to one of the preceding claims, characterized in that it comprises an impact modifier agent.
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