EP2571925A1 - Composite polyamide article - Google Patents

Composite polyamide article

Info

Publication number
EP2571925A1
EP2571925A1 EP11723366A EP11723366A EP2571925A1 EP 2571925 A1 EP2571925 A1 EP 2571925A1 EP 11723366 A EP11723366 A EP 11723366A EP 11723366 A EP11723366 A EP 11723366A EP 2571925 A1 EP2571925 A1 EP 2571925A1
Authority
EP
European Patent Office
Prior art keywords
polyamide
acid
monomers
hydroxyaromatic
polyamides
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.)
Withdrawn
Application number
EP11723366A
Other languages
German (de)
French (fr)
Inventor
Franck Touraud
Gilles Orange
Stéphane JEOL
Roland Durand
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.)
Rhodia Operations SAS
Original Assignee
Rhodia Operations SAS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Rhodia Operations SAS filed Critical Rhodia Operations SAS
Publication of EP2571925A1 publication Critical patent/EP2571925A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D177/06—Polyamides derived from polyamines and polycarboxylic acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/40—Shaping or impregnating by compression not applied
    • B29C70/42—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles
    • B29C70/46—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using matched moulds, e.g. for deforming sheet moulding compounds [SMC] or prepregs
    • B29C70/465—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using matched moulds, e.g. for deforming sheet moulding compounds [SMC] or prepregs and impregnating by melting a solid material, e.g. sheets, powders of fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/40—Shaping or impregnating by compression not applied
    • B29C70/42—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles
    • B29C70/46—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using matched moulds, e.g. for deforming sheet moulding compounds [SMC] or prepregs
    • B29C70/48—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using matched moulds, e.g. for deforming sheet moulding compounds [SMC] or prepregs and impregnating the reinforcements in the closed mould, e.g. resin transfer moulding [RTM], e.g. by vacuum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/40—Shaping or impregnating by compression not applied
    • B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
    • B29C70/52—Pultrusion, i.e. forming and compressing by continuously pulling through a die
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • 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
    • 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
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/125—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyamides
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer

Definitions

  • the present invention relates to the use of polyamide modified with hydroxyaromatic compounds for impregnating reinforcing materials in the form of fabric of industrial fabrics for the manufacture of composite materials.
  • the field of the invention is that of composite materials and their manufacturing processes.
  • the invention also relates to a method of manufacturing a composite article comprising at least:
  • thermosetting resins In the field of high-performance materials, composites have taken a prominent place, due to their performance and the weight gains they allow.
  • the best known high-performance composites to date are obtained from thermosetting resins, the use of which is limited to low to medium series applications, mainly in aeronautics, motor sports, and in the best cases, presenting manufacturing times of about fifteen minutes, for example, during the manufacture of skis.
  • the cost of these materials, and / or the manufacturing time make them difficult to compatible with mass use.
  • the use of thermosetting resins often involves the presence of solvents and monomers. Finally, these composites are difficult to recycle.
  • Thermoplastic polymers are generally known for their high viscosity, which is a drag on the impregnation of materials reinforcement, generally composed of very dense multifilamentary bundles. It results from the use of thermoplastic matrices available on the market, a difficulty of impregnation requiring either prolonged impregnation times or significant application pressures. In most cases, the composite materials obtained from these matrices may have microvoids and non-impregnated areas. These microvids cause mechanical properties to drop, premature aging of the material and problems of delamination when the material consists of several layers of reinforcements. This phenomenon of loss of mechanical properties is also accentuated when the cycle times for the manufacture of composite articles decrease.
  • Another problem frequently encountered with polymer matrix composite materials is their resistance to aging, and more particularly to hygrothermal aging.
  • the diffusion of water within the composite materials causes a significant change in certain physical characteristics such as, for example, the glass transition temperature or swelling of the matrix.
  • a modification at the matrix / fiber interfaces can also be observed, generally with an irreversible character.
  • This aging is manifested by a degradation of the mechanical performances, in particular the resistance to breakage. It is then necessary to oversize the parts, which leads to an increase in weight and significant additional cost.
  • the objective of the present invention is therefore to remedy these drawbacks by proposing a composite article that can be manufactured with short cycle times while having good use properties, such as good mechanical properties and good resistance to wear. hygrothermal aging.
  • polyamide resin modified with hydroxyaromatic compounds for the manufacture of composite articles made it possible to obtain articles having not only good mechanical properties, such as in particular rigidity, breaking strength, impact resistance, and fatigue behavior, even when manufactured with shorter cycle times than those usually used, and without any other treatment, but also good resistance to hygrothermal aging.
  • This makes it possible to provide a composite material which has both the advantage of reducing manufacturing costs, the use of tools implementing shortened cycle times, and also sufficient durability for structural applications.
  • Composite articles according to the present invention also exhibit low water uptake and good dimensional stability.
  • These composite articles have in particular a very good maintenance of mechanical properties after hygrothermal aging, particularly compared to conventional composite polyamide articles.
  • the articles according to the invention have in particular the advantages of rigidity, lightness, and recyclability, and a good surface appearance. These articles also have good fireproofing properties.
  • the invention firstly relates to a method of manufacturing a composite article comprising at least:
  • the present invention also relates to a composite article comprising at least one reinforcing fabric and a modified polyamide containing patterns. hydroxyaromatic chemically bonded to the polyamide chain, and a novolac resin.
  • fabric is meant a textile surface of yarns or fibers possibly joined together by any method, such as, in particular, gluing, felting, braiding, weaving or knitting. These fabrics are also referred to as fibrous or filamentary networks.
  • wire is meant a monofilament, a continuous multifilament yarn, a spun yarn, obtained from a single type of fiber or several types of fibers in intimate mixture. The continuous wire can also be obtained by assembling several multifilament yarns.
  • fiber is meant a filament or a set of cut, cracked or converted filaments.
  • the yarns and / or reinforcing fibers according to the invention are preferably chosen from yarns and / or fibers of carbon, glass, aramids, polyimides, flax, hemp, sisal, coir and jute. , kenaf and / or their mixture. More preferably, the reinforcement fabrics consist solely of yarns and / or reinforcing fibers chosen from among the yarns and / or the fibers of carbon, glass, aramids, polyimides, flax, hemp, sisal, coir, jute, kenaf and / or their mixture.
  • These fabrics are preferably a grammage, that is to say the weight per square meter, between 100 and 1000 g / m 2 .
  • Their structure can be random, unidirectional (1D), or multidirectional (2D, 2,5D, 3D or other).
  • a composite article according to the invention may comprise several reinforcing fabrics of different nature or not.
  • the fabrics may optionally be coated or sized, in particular to provide special features.
  • the polyamide according to the invention advantageously has a melt viscosity ⁇ less than 250 Pa.s, preferably between 1 and 50 Pa.s. This viscosity can be measured using a planar planar rheometer with a diameter of 50 mm, under a shear streaking sweep ranging from 1 to 160 s-1.
  • the polymer is in the form of a film with a thickness of 150 ⁇ , granules or powder. The polymer is brought to a temperature of 25 to 30 ° C above its melting point, and the measurement is then carried out.
  • the number-average molecular weight (Mn) of the polyamides is preferably greater than 6000 g / mol, more preferably between 8000 g / mol and 20000 g / mol, having sufficient mechanical properties and a certain resistance during the various methods of setting up. form.
  • Semi-crystalline polyamides are particularly preferred.
  • the present invention relates in particular to a polyamide modified with a compound containing at least one aromatic hydroxyl group chemically bonded to the polymer chain, this polyamide being obtainable by polymerization, in addition to the monomers of the polyamide, of a hydroxyaromatic compound or by melt-phase mixing of a polyamide partially or totally formed with a hydroxyaromatic compound, in particular during a reactive extrusion.
  • the modified polyamide according to the invention can also be obtained by solid phase polycondensation or solvent phase for certain polyamides.
  • the monomers of the polyamides may in particular be diacid monomers, in particular aliphatic, cycloaliphatic, arylaliphatic or aromatic monomers, diamine monomers, in particular aliphatic monomers, and / or amino acids or lactams.
  • diacid monomers in particular aliphatic, cycloaliphatic, arylaliphatic or aromatic monomers
  • diamine monomers in particular aliphatic monomers
  • / or amino acids or lactams are generally the monomers conventionally used for the production of semi-crystalline polyamides, such as aliphatic polyamides, semi-aromatic polyamides and, more generally, linear polyamides obtained by polycondensation between a saturated diacid aliphatic or aromatic, and a primary saturated aromatic or aliphatic diamine, the polyamides obtained by condensation of a lactam, an amino acid or linear polyamides obtained by condensation of a mixture of these different monomers.
  • these copolyamides may be, for example, hexamethylene polyadipamide, polyphthalamides obtained from terephthalic and / or isophthalic acid, copolyamides obtained from adipic acid, hexamethylenediamine and caprolactam.
  • the monomers of the polyamides may optionally contain unsaturations or heteroatoms such as oxygen, sulfur or nitrogen.
  • polyamides chosen from the group comprising polyamide 6, polyamide 66, polyamide 6.10, polyamide 11, polyamide 12, polyamide 6.12, poly (meta-xylylene adipamide) (MXD6), polyamide may be used.
  • the composition of the invention may also comprise copolyamides derived in particular from the above polyamides, or mixtures of these polyamides or copolyamides.
  • the preferred polyamides are polyhexamethylene adipamide, polycaprolactam, or copolymers and blends between polyhexamethylene adipamide and polycaprolactam.
  • the dicarboxylic acids may also be chosen from glutaric acid, adipic acid, pimellic acid, suberic acid, azelaic acid, sebacic acid and dodecanedioic acid; 1,2-or 1,3-cyclohexane dicarboxylic acid; 1,2-or 1,3-phenylene diacetic acid; 1, 2-or 1,3-cyclohexane diacetic acid; isophthalic acid; terephthalic acid; 4,4'-benzophenone dicarboxylic acid; 2,5-naphthalene dicarboxylic acid; and pt-butyl isophthalic acid.
  • the preferred dicarboxylic acid is adipic acid.
  • the diamines may for example be chosen from hexamethylenediamine; butane diamine; pentane diamine; 2-methyl pentamethylene diamine; 2-methyl hexamethylenediamine; 3-methyl hexamethylene diamine; 2,5-dimethyl hexamethylenediamine; 2,2-dimethylpentamethylenediamine; nonane diamine; decanediamine; 5-methylnonanediamine; dodecamethylene diamine; 2,2,4- and 2,4,4-trimethyl hexamethylenediamine; 2,2,7,7-tetramethyl octamethylene diamine; isophorone diamine; diaminodicyclohexyl methane and C2-C16 aliphatic diamines which may be substituted by one or more alkyl groups.
  • the preferred diamine is hexamethylenediamine.
  • the modified polyamide of the invention can be obtained from, in particular, a lactam monomer or an amino acid, preferably an aliphatic one.
  • lactams or amino acids mention may be made of caprolactam, 6-aminohexanoic acid, 5-aminopentanoic acid, 7-aminoheptanoic acid, 11-aminoundecanoic acid and dodecanolactam.
  • polyamides may in particular be modified with difunctional or monofunctional monomers, such as especially diacids or diamines, monoacids or monoamines.
  • Polyfunctional molecules at least trifunctional, may also be used to provide branches or connections to the polyamide.
  • bishexamethylenetriamine is mentioned.
  • Polyamides according to the invention may also be obtained by mixing, in particular melt, polyamides with chain length-changing monomers, such as in particular diamines, dicarboxylic acids, monoamines and / or mono carboxylic acids.
  • the composition of the invention may also comprise copolyamides derived in particular from the above polyamides, or mixtures of these polyamides or (co) polyamides. It is also possible to use, as high-flow polyamide, a star polyamide comprising star macromolecular chains and, where appropriate, linear macromolecular chains.
  • the star-shaped polyamide is a polymer comprising star macromolecular chains, and optionally linear macromolecular chains, the polymers comprising such star macromolecular chains are for example described in the documents FR2743077, FR2779730, EP0682057 and EP0832149. These compounds are known to exhibit improved fluidity over linear polyamides.
  • the star macromolecular chains comprise a core and at least three branches of polyamide.
  • the branches are linked to the heart by a covalent bond, via an amide group or a group of another nature.
  • the core is an organic or organometallic chemical compound, preferably a hydrocarbon compound optionally comprising heteroatoms and to which the branches are connected.
  • the branches are polyamide chains.
  • the polyamide chains constituting the branches are preferably of the type obtained by polymerization of lactams or amino acids, for example of the polyamide 6 type.
  • the polyamide star structure according to the invention optionally comprises, in addition to star chains, linear polyamide chains.
  • the ratio by weight between the quantity of star chains and the sum of the quantities of star and linear chains is between 0.5 and 1 inclusive. It is preferably between 0.6 and 0.9.
  • carboxylic acid means carboxylic acids and their derivatives, such as acid anhydrides, acid chlorides, amides or esters. Processes for obtaining these star polyamides are described in documents FR2743077 and FR2779730. These processes lead to the formation of star macromolecular chains, in mixture with possibly linear macromolecular chains.
  • the composition according to the invention preferably has from 30 to 75% by volume of polyamide, relative to the total weight of the composition, preferably from 35 to 60% by volume.
  • the hydroxyaromatic compound is a compound carrying at least one, in particular one or two, functions capable of reacting with the amine or acid functional groups of the polyamide or of the monomers of the polyamide.
  • aromatic hydroxyl group is meant a hydroxyl function attached to a carbon atom forming part of an aromatic ring.
  • hydroxyaromatic compound is meant an organic compound having at least one aromatic hydroxyl group.
  • chemically linked is meant bound by a covalent bond. Once chemically bonded to the polyamide chain, the hydroxyaromatic compound becomes a hydroxyaromatic unit and the modified polyamide of the invention is a polyamide containing hydroxyaromatic units.
  • the functions of the hydroxyaromatic compound that can react with the functions of the polyamide include the acid, ketone, amine and aldehyde functions.
  • acid function is meant a carboxylic acid or derivative function, such as acid chloride, acid anhydride, amide, ester.
  • the aromatic hydroxyl groups of the invention are not considered to be functions reactive with acid functions.
  • the hydroxyl group of the monomer is not congested, that is to say for example that the carbon atoms located at a of the hydroxyl function are preferably not substituted by bulky substituents, such as branched alkyls.
  • the hydroxyaromatic compound may for example be represented by the following formula (I):
  • Z is a multivalent aromatic or arylaliphatic hydrocarbon radical (at least divalent)
  • x is from 1 to 10;
  • F is an acid, aldehyde, amine, ketone function capable of binding to an acid or amine function of the monomers of the polyamide, and
  • n is between 1 and 5.
  • Z may for example be selected from the group consisting of: benzene, methyl benzene, naphthalene, biphenyl, diphenyl ether, diphenyl sulfide, diphenyl sulfone, ditolyl ether, xylylene, diethyl benzene, or pyridine .
  • arylaliphatic radical is meant a radical according to which at least one F function of the compound of formula (I) is not attached to this radical by a carbon atom forming part of an aromatic ring.
  • Advantageously Z has between 6 and 18 carbon atoms.
  • a hydroxyaromatic compound can perfectly contain several types of F functions of different nature.
  • This compound is preferably selected from the group consisting of: 2-hydroxyterephthalic acid, 5-hydroxyisophthalic acid, 4- hydroxyisophthalic acid, 2,5-dihydroxyterephthalic acid, 4-hydroxyphenylacetic acid or gallic acid, L-Tyrosine, 4-hydroxyphenylacetic acid, 3,5-diaminophenol, 5-hydroxy-m-xylylene diamine 3-Anninophenol, 3-amino-4-methylphenol, and 3-hydroxy-5-amino benzoic acid.
  • the molar proportion of hydroxyaromatic compound relative to all the monomers constituting the polyamide is generally between 0.1 and 100%, preferably between 1 and 70. %, more preferably between 0.5 and 60%, more preferably between 2.5 and 50%.
  • the polyamide of the invention is especially obtained by a melt polymerization process of the various monomers described above, these monomers being present in whole or in part.
  • melt polymerization it is meant that the polymerization is carried out in the liquid state, and that the polymerization medium contains no solvent other than water, possibly.
  • the polymerization medium may for example be an aqueous solution comprising the monomers, or a liquid comprising the monomers.
  • the polymerization medium comprises water as a solvent. This facilitates the agitation of the medium, and therefore its homogeneity.
  • the polymerization medium may also include additives such as chain limiters.
  • the modified polyamide of the invention is generally obtained by polycondensation between the various monomers, present in whole or in part, to form polyamide chains, with formation of the elimination product, in particular water, a part of which can vaporize .
  • the modified polyamide of the invention is generally obtained by heating at high temperature and pressure, for example an aqueous solution comprising the monomers, or a liquid comprising the monomers, to evaporate the elimination product, in particular water (initially present in the polymerization medium and / or or formed during the polycondensation) while avoiding any formation of solid phase to avoid caking.
  • the polycondensation reaction is generally carried out at a pressure of about 0.5-3.5 MPa (0.5-2.5 MPa) at a temperature of about 100-320 ° C (180-300 ° C).
  • the polycondensation is generally continued in the melt phase at atmospheric pressure or reduced so as to reach the desired degree of advancement.
  • the polycondensation product is a molten polymer or prepolymer. It may comprise a vapor phase consisting essentially of vapor of the elimination product, in particular water, which may have been formed and / or vaporized.
  • This product can be subjected to vapor phase separation and finishing steps to achieve the desired degree of polycondensation.
  • the separation of the vapor phase may for example be carried out in a cyclone device. Such devices are known.
  • the finish consists in maintaining the polycondensation product in the molten state, at a pressure close to atmospheric pressure or under reduced pressure, for a time sufficient to reach the desired degree of advancement. Such an operation is known to those skilled in the art.
  • the temperature of the finishing step is advantageously greater than or equal to 100 ° C. and in all cases greater than the solidification temperature of the polymer.
  • the residence time in the finishing device is preferably greater than or equal to 5 minutes.
  • the polycondensation product can also undergo a solid phase postcondensation step. This step is known to those skilled in the art and makes it possible to increase the degree of polycondensation to a desired value.
  • the process of the invention is similar in its conditions to the conventional method for preparing polyamide of the type of those obtained from dicarboxylic acids and diamines, in particular the process for producing polyamide 66 from adipic acid and from hexamethylene diamine.
  • This method of manufacturing polyamide 66 is known to those skilled in the art.
  • the process for producing polyamide of the type of those obtained from dicarboxylic acids and diamines generally uses as raw material, a salt obtained by a mixture in stoichiometric quantity, generally in a solvent such as water, a diacid with a diamine.
  • adipic acid is mixed with hexamethylene diamine generally in water to obtain hexamethylene diammonium adipate better known as nylon salt or " Salt N ".
  • these compounds can be introduced, at least in part, in the form of a salt.
  • the diacid is adipic acid and diamine hexamethylenediamine
  • these compounds can be introduced at least partly in the form of N salt. This makes it possible to have a stoichiometric equilibrium.
  • the hydroxyaromatic compound is a diacid or a diamine, it is also possible to introduce it in the form of salts, with a diamine or a diacid.
  • the process of the invention generally leads to a random polymer when the hydroxyaromatic compound is polyfunctional, especially at least difunctional, and to a polyamide having partially or completely hydroxyaromatic terminations, when the hydroxyaromatic compound is monofunctional.
  • the modified polyamide obtained at the end of the finishing step can be cooled and granulated.
  • the modified polyamide obtained by the process of the invention in molten form can be directly shaped or extruded and granulated, for subsequent shaping after melting.
  • the modified polyamide according to the invention can be used as a matrix, alone or in combination with other thermoplastic polymers, in particular polyamides, polyesters, or polyolefins.
  • the polyamide composition according to the invention is especially used as a matrix, in particular by granulation, calendering, extrusion in the form of a film, grinding, injection, molding, injection molding, pressing, and others.
  • the impregnation step of the polyamide composition of the invention and the reinforcing fabric can be carried out in various ways, according to various possible methods. It is perfectly possible to impregnate one or more reinforcing fabric.
  • the melt polyamide composition may be injected into a molding chamber comprising at least one or more reinforcing fabrics.
  • the inside of the molding chamber is at a temperature of plus or minus 50 ° C with respect to the melting temperature of said polyamide. It is then possible to cool the molding chamber and the article obtained to finally recover said article.
  • This process is also known as the thermoset resin transfer molding process (RTM), which consists in injecting resin into a closed mold in which reinforcement fibers have been previously placed. This process can be carried out under pressure.
  • a composite article according to the invention by a "film stacking" method which consists in a temperature compression of a stack of reinforcement fabrics and polyamide films.
  • one or more reinforcing fabrics and one or more films are brought into contact with one another. of polyamide modified with hydroxyaromatic compounds and impregnation of the fabrics by melting the polyamide.
  • the necessary pressures for a good assembly are generally higher than 30 bar.
  • the composite article according to the invention may also be produced by bringing one or more reinforcing fabrics into contact with the powder of a polyamide as defined above, in particular of the fine powder, and the said impregnation is carried out. by melting the polyamide at a temperature equal to or greater than that of the melting point of the polyamide, optionally under pressure.
  • the composite article of the invention can also be made by pultrusion. This technique generally involves drawing through a heated die one or more continuous yarns and fibers so as to impregnate it with a molten thermoplastic resin to obtain a rod or finished or semi-finished article.
  • the article After impregnation of the reinforcing fabric with the polyamide, the article is obtained by solidification of the matrix.
  • the cooling can advantageously be carried out rapidly so as to avoid significant crystallization of the polyamide, in particular to maintain the properties of the article.
  • the cooling can in particular be carried out in less than 5 minutes, more preferably in less than one minute.
  • the mold may for example be cooled by a cold fluid circuit. It is also possible to transfer the composite article to a cold mold, possibly under pressure.
  • the polyamide composition and / or the composite article according to the invention may also comprise all the additives normally used in polyamide-based compositions used for the manufacture of articles.
  • additives include thermal stabilizers, UV stabilizers, antioxidants, lubricants, pigments, dyes, plasticizers, reinforcing fillers, impact modifiers, and coupling agents.
  • additives to improve the quality of the polyamide reinforcing fabric interfaces can also be used. These additives may for example be incorporated into the polyamide composition, incorporated into the threads and / or fibers of the reinforcing fabric, present on the threads and / or fibers of said fabric, or else deposited on the reinforcing fabric.
  • additives may be coupling agents such as those of aminosilane or chlorosilane type, or fluidizing or wetting agents, or their combination.
  • Reinforcing fillers may be incorporated in the polyamide composition. These fillers may be chosen from fibrous fillers, such as short glass fibers, for example, or non-fibrous fillers such as kaolin, talc, silica, mica or wollastonite. Their size is generally between 1 and 25 ⁇ . Sub-micron or even nanometric charges may also be used, alone or in addition to other charges.
  • the polyamide composition comprises a novolac resin. It may comprise one or more types of different novolac resin.
  • novolac resin is generally understood to mean a phenolic resin whose formaldehyde / phenol ratio is less than 1 and which therefore remains normally thermoplastic until it is heated with an appropriate quantity of a compound, for example formaldehyde or hexamethylenetetramine, which may give additional bonds, thus giving an infusible product.
  • Novolak resins are generally condensation products of phenolic compounds with aldehydes or ketones. These condensation reactions are generally catalyzed by an acid or a base.
  • the novolak resins generally have a degree of condensation of between 2 and 15.
  • the phenolic compounds can be chosen alone or as a mixture from phenol, cresol, xylenol, naphthol, alkylphenols, such as butyl phenol, terbutylphenol, isooctylphenol, nitrophenol, phenylphenol, resorcinol or biphenol A; or any other substituted phenol.
  • aldehyde The most frequently used aldehyde is formaldehyde. However, others may be used, such as acetaldehyde, paraformaldehyde, butyraldehyde, crotonaldehyde, glyoxal, and furfural.
  • ketone it is possible to use acetone, methyl ethyl ketone or acetophenone.
  • the aldehyde and / or the ketone may optionally carry another functional group, such as, for example, a carboxylic acid function. For example, glyoxylic acid or levulinic acid may be mentioned.
  • the novolak resin is a condensation product of phenol and formaldehyde.
  • the novolak resins used advantageously have a molecular weight of between 500 and 3000 g / mol, preferably between 800 and 2000 g / mol.
  • the composition according to the invention may comprise from 1 to 20% by weight of novolac resin, especially from 1 to 10% by weight, relative to the total weight of the composition.
  • the present invention relates to an article obtainable by the method of the invention.
  • the article may in particular be a polyamide-based composite article comprising a reinforcing fabric, in which the polyamide has a melt viscosity ⁇ of between 1 and 50 Pa.s.
  • the articles according to the invention preferably comprise between 25 and 80% by volume of reinforcing fabric with respect to the total weight.
  • the articles of the invention may be finished or semi-finished articles which may also be called prepregs. For example, it is possible to thermoform composite articles in the form of plates to give them a defined shape after cooling.
  • the invention thus relates to composite articles or preforms that can be obtained by the method according to the present invention.
  • the articles of the invention may also be sandwich type structures having a core inserted between two skins.
  • the composites of the invention can be used to form the outer layers, by associating them with a core type honeycomb or foam type.
  • the layers can be assembled by chemical or thermal bonding.
  • Composite structures according to the invention can be used in many fields such as aeronautics, automotive, energy, electrical industry, sports and leisure industry. These structures can be used to make sports articles such as skis or to achieve various surfaces such as special floors, partitions, vehicle bodies, or billboards. In aeronautics these structures are used in particular at fairings (fuselage, wing, empennage). In the automobile, they are used for example at floors, supports such as rear shelves, or at the level of structural parts.
  • a specific language is used in the description so as to facilitate understanding of the principle of the invention. It should nevertheless be understood that no limitation of the scope of the invention is envisaged by the use of this specific language. In particular, modifications, improvements and improvements may be considered by a person familiar with the technical field concerned on the basis of his own general knowledge.
  • the term and / or includes the meanings and, or, as well as all other possible combinations of elements connected to this term.
  • Acid end group (GTC) and amine (GTA) endpoints assayed by potentiometry, expressed in meq / kg.
  • the phenol GTP terminal group contents (for the monofunctional hydroxyaromatic compounds) are determined from the initial amounts of reagents introduced into the synthesis reactor.
  • T f Melting temperature
  • T c cooling crystallization temperature
  • T g Glass transition temperature
  • These polyamides were characterized by melt viscosity measurements made on an Ares (Rheometrics) plane-plane rheometer at 280 ° C.
  • the viscosity curves as a function of the shear rate show that the polymers under consideration have a Newtonian behavior in the shear rate range between 1 and 150 s-1: the viscosity retained is the plateau value (between 1 and 150 s -1). 1).
  • the reinforcements used in the examples are in the form of glass fabric preforms, cut to the dimensions required for the manufacture of the plates, that is to say 150 ⁇ 150 mm or 200 ⁇ 300 mm.
  • the reinforcing fabric used is a fiberglass fabric (0 ° -90 °) of Synteen & Luckenhaus origin from a roving of 1200 tex, having a basis weight of 600 g / m 2 .
  • the comparative polyamide C1 used in the examples is a high fluidity polyamide 6.6 having an IV viscosity index of 97 mL / g, a melt viscosity ⁇ of 30 Pa.s and a Mn of 1100 g / mol.
  • the polymer obtained is cast in the form of rod, cooled and granulated by cutting rushes.
  • the copolyamide has a higher Tg of 6.2 ° C than that of PA 66.
  • the polymer obtained is cast in the form of rod, cooled and granulated by cutting rushes.
  • the copolyamide has a higher Tg of 15.2 ° C than that of PA 66.
  • This copolyamide has a melt viscosity ⁇ of 37 Pa.s.
  • Example 3 Preparation of a PA 6HIA Polyamide and of PA 66 / PA 6HIA 85/15 by Weight
  • a 51% by weight 6HIA salt in water is made by mixing a stoichiometric amount of hexamethylene diamine and 5-hydroxyisophthalic acid in water.
  • 5623 g of 51% 6HIA salt, 12.1 g of 99.5% 5-hydroxyisophthalic acid, 105 g of water and 3.3 g of antifoaming agent are then introduced into a polymerization reactor.
  • Polyamide PA 6HIA is manufactured according to a standard polyamide 66 polymerization process, with 30 minutes of finishing.
  • the polymer obtained is cast in the form of rod, cooled and granulated by cutting rushes.
  • the PA 66 and the PA 6HIA thus prepared are mixed in a proportion of 85/15 by weight in the melt in a DSM MIDI 2000 micro-compounder ("micro-compounder”) (15 cm 3 ) at a temperature of 275 ° C.
  • This mixture has a melt viscosity ⁇ of 35 Pa.s.
  • the polyamide is manufactured according to a standard polyamide 66 polymerization process with 30 minutes of finishing.
  • the polymer obtained is cast in the form of rod, cooled and granulated by cutting rushes.
  • GTC 103.3 meq / kg
  • GTA 29.4 meq / kg
  • the theoretical amount of phenol functions at the GTP chain end is calculated from the initial amounts introduced into the reactor.
  • GTP 437 meq / kg.
  • the various polymers considered are used in powder form for the most fluid, if not in film form.
  • the powders are obtained by cryogenic grinding, either in dry ice or in liquid nitrogen.
  • the films are made by extrusion of granules on a Leistritz twin-screw extruder 34 and L / D 34 equipped with a flat die and a film-forming machine (extruder flow rate 10 Kg / h, screw speed 250 rpm; temperature of 270 ° C).
  • the spacing of the lips of the die is about 300 ⁇ for a width of 30 cm with a call speed of 3.2 m / min on rolls regulated at 1 15 ° C: the films obtained have a thickness that varies between 160 and 180 ⁇ (coils of width 300 mm).
  • the polymer films are cut into sheets of 150x150 mm or 200x300 mm, from the previously obtained coils. It is the same for reinforcement fabrics.
  • Composite parts are produced using a Schwabenthan (Polystat 300A) temperature-controlled dual-plate hydraulic press: hot plates (heating resistors) and cooled trays (water circulation).
  • a metal mold with a print size of 150 mm x 150 mm or 200x300 mm is used.
  • a preform consisting of an alternating stack comprising 6 sheets of glass fabric and between each is a polymer sheet, or evenly distributed powder, the two outer layers being sheets of glass fabrics.
  • the temperature of the platens of the press is previously raised to 290 ° C before the introduction of the preform. At this temperature, the pressure is applied between 1 and 50 bar and maintained at this value; degassing is done quickly.
  • the assembly is maintained at the same temperature and pressure, without degassing. Again, it is then carried out a series of degassing, then a maintenance always at the same temperature and pressure.
  • the mold is then transferred to the cooled platen device and maintained at a pressure of between 1 and 50 bar.
  • the composite parts thus obtained have a dimension of 150 ⁇ 150 mm or 200 ⁇ 300 mm and a thickness of about 2 mm.
  • the sheets 150x150 mm or 200x300 mm are cut to obtain samples of dimensions 150x20x2 mm.
  • a first series of samples are characterized just after manufacture (sample placed in a sealed envelope, in order to keep them in a dry state RHO).
  • a conditioning treatment can also be carried out according to the ISO1 1 10 standard "plastic / polyamide / accelerated conditioning of specimens": state said RH50.
  • the equilibrium water content is obtained by conditioning the composite parts with a cycle of 14 days, at 70 ° C. under a residual humidity RH of 62%.
  • the 3-point bending tests at room temperature are carried out on parallepipedic specimens (150x20x2 mm), according to ISO standard No. 14125, on a ZWICK 1478 machine: 64 mm center distance, 5 mm / min crosshead speed. Young's elastic modulus E (GPa) and maximum stress ⁇ max (MPa) values are measured and calculated. Direct tensile tests at room temperature are carried out on parallelepipedal specimens (250x25x2mm), according to ASTM D3039 / D3039M on a ZWICK 1478 machine: crosshead speed of 1 to 5 mm / min. The elastic modulus values of Young E (GPa) and amax peak stress (MPa) are measured and calculated.
  • Constraint Module Constraint Module
  • PA 2 RHO 28 590 - - In the case of a 5 minute manufacturing cycle under average pressure, the mechanical performances obtained are high: max stress (peak) in bending of 550 to 650 MPa, for modulus values between 27 to 29 GPa.
  • max stress (peak) in bending of 550 to 650 MPa For the modified polyamides containing 6HIA hydroxyaromatic units, there is a slight improvement in performance at the breaking stress.
  • the tensile failure mode is significantly more abrupt than in the case of unmodified polyamides.
  • the samples prepared according to Example 6 were subjected to hygrothermal aging. Accelerated type aging was performed by immersing the samples in water at 80 ° C. for 8 days (accelerated test).
  • test pieces were either tested as is, or reconditioned by removal of the adsorbed water: treatment at 80 ° C under vacuum for 24 hours (dry state: RHO).

Abstract

The present invention relates to the use of a polyamide modified by hydroxyl aromatic compounds used to impregnate reinforcement materials assuming the form of industrial fabric cloth for manufacturing composite materials. The field of the invention is that of composite materials and the methods for manufacturing same. The invention likewise relates a method for manufacturing a composite article including at least: a) a step of impregnating a reinforcing cloth with a polyamide composition in the molten state, said polyamide includes hydroxy aromatic units which are chemically linked to the polyamide chain; the composition includes a novolac resin; and b) a step of cooling and then recovering the composite article.

Description

Article polyamide composite  Composite polyamide article
La présente invention concerne l'utilisation de polyamide modifié par des composés hydroxyaromatiques servant à l'imprégnation de matériaux de renfort prenant la forme d'étoffe de tissus industriels pour la fabrication de matériaux composites. Le domaine de l'invention est celui des matériaux composites et de leurs procédés de fabrication. L'invention concerne également un procédé de fabrication d'un article composite comprenant au moins : The present invention relates to the use of polyamide modified with hydroxyaromatic compounds for impregnating reinforcing materials in the form of fabric of industrial fabrics for the manufacture of composite materials. The field of the invention is that of composite materials and their manufacturing processes. The invention also relates to a method of manufacturing a composite article comprising at least:
a) une étape d'imprégnation d'une étoffe de renfort avec une composition polyamide à l'état fondu, ledit polyamide comprend des motifs hydroxyaromatiques chimiquement liés à la chaîne du polyamide, la composition comprenant une résine novolaque ; a) a step of impregnating a reinforcing fabric with a polyamide melt composition, said polyamide comprises hydroxyaromatic units chemically bonded to the polyamide chain, the composition comprising a novolak resin;
b) une étape de refroidissement et ensuite de récupération de l'article composite. b) a step of cooling and then recovering the composite article.
ART ANTERIEUR PRIOR ART
Dans le domaine des matériaux hautes-performances, les composites ont pris une place prépondérante, de par leurs performances et les gains de poids qu'ils autorisent. Les composites hautes performances les plus connus à ce jour, sont obtenus à partir de résines thermodurcissables, dont l'utilisation est limitée aux applications de faibles à moyennes séries, principalement dans l'aéronautique, le sport automobile, et dans les meilleurs cas, présentant des temps de fabrication voisins d'une quinzaine de minutes, comme par exemple, lors de la fabrication de skis. Le coût de ces matériaux, et/ou les temps de fabrication, les rendent difficilement compatibles avec un usage en grande série. De plus, l'utilisation de résines thermodurcissables implique souvent la présence de solvants et de monomères. Enfin, ces composites sont difficilement recyclables.  In the field of high-performance materials, composites have taken a prominent place, due to their performance and the weight gains they allow. The best known high-performance composites to date are obtained from thermosetting resins, the use of which is limited to low to medium series applications, mainly in aeronautics, motor sports, and in the best cases, presenting manufacturing times of about fifteen minutes, for example, during the manufacture of skis. The cost of these materials, and / or the manufacturing time, make them difficult to compatible with mass use. In addition, the use of thermosetting resins often involves the presence of solvents and monomers. Finally, these composites are difficult to recycle.
Les polymères thermoplastiques sont en général connus pour leur viscosité élevée, ce qui constitue un frein en ce qui concerne l'imprégnation des matériaux de renfort, composés en général de faisceaux multifilamentaires très denses. Il résulte de l'emploi des matrices thermoplastiques disponibles sur le marché, une difficulté d'imprégnation nécessitant soit des temps d'imprégnation prolongés, soit des pressions de mise en œuvre importantes. Dans la majeure partie des cas, les matériaux composites obtenus à partir de ces matrices peuvent présenter des microvides et des zones non imprégnées. Ces microvides causent des chutes de propriétés mécaniques, un vieillissement prématuré du matériau ainsi que des problèmes de délaminage lorsque le matériau se compose de plusieurs couches de renforts. Ce phénomène de perte de propriétés mécaniques est par ailleurs accentué lorsque les temps de cycle pour la fabrication des articles composites diminuent. Thermoplastic polymers are generally known for their high viscosity, which is a drag on the impregnation of materials reinforcement, generally composed of very dense multifilamentary bundles. It results from the use of thermoplastic matrices available on the market, a difficulty of impregnation requiring either prolonged impregnation times or significant application pressures. In most cases, the composite materials obtained from these matrices may have microvoids and non-impregnated areas. These microvids cause mechanical properties to drop, premature aging of the material and problems of delamination when the material consists of several layers of reinforcements. This phenomenon of loss of mechanical properties is also accentuated when the cycle times for the manufacture of composite articles decrease.
Un autre problème fréquemment rencontré avec les matériaux composites à matrice polymère est leur tenue au vieillissement, et plus particulièrement au vieillissement hygrothermique. La diffusion d'eau au sein des matériaux composites entraîne une modification sensible de certaines caractéristiques physiques comme par exemple la température de transition vitreuse ou un gonflement de la matrice. Une modification au niveau des interfaces matrice/fibres peut également être observée, avec généralement un caractère irréversible. Ce vieillissement se manifeste par une dégradation des performances mécaniques, notamment la tenue à la rupture. Il est alors nécessaire de surdimensionner les pièces, ce qui entraîne une augmentation de poids et un surcoût non négligeable. Another problem frequently encountered with polymer matrix composite materials is their resistance to aging, and more particularly to hygrothermal aging. The diffusion of water within the composite materials causes a significant change in certain physical characteristics such as, for example, the glass transition temperature or swelling of the matrix. A modification at the matrix / fiber interfaces can also be observed, generally with an irreversible character. This aging is manifested by a degradation of the mechanical performances, in particular the resistance to breakage. It is then necessary to oversize the parts, which leads to an increase in weight and significant additional cost.
L'objectif de la présente invention est donc de remédier à ces inconvénients en proposant un article composite qui puisse être fabriqué avec des temps de cycle courts tout en ayant de bonnes propriétés d'usage, telles que de bonnes propriétés mécaniques et une bonne tenue au vieillissement hygrothermique. The objective of the present invention is therefore to remedy these drawbacks by proposing a composite article that can be manufactured with short cycle times while having good use properties, such as good mechanical properties and good resistance to wear. hygrothermal aging.
INVENTION INVENTION
La demanderesse a découvert de manière inattendue que l'utilisation de résine polyamides modifiées par des composés hydroxyaromatiques pour la fabrication d'articles composites permettaient l'obtention d'articles présentant non seulement de bonnes propriétés mécaniques, telles que notamment la rigidité, la résistance à la rupture, la résistance aux chocs, et le comportement en fatigue, même lorsqu'ils sont fabriqués avec des temps de cycle plus courts que ceux habituellement utilisés, et sans aucun autre traitement, mais également une bonne tenue au vieillissement hygrothermique. Ceci permet de fournir un matériau composite présentant à la fois un avantage de réduction de coûts de fabrication, par l'emploi d'un outillage mettant en œuvre des temps de cycles raccourcis, et également une durabilité suffisante pour les applications de structure. Les articles composites selon la présente invention présentent également une faible reprise en eau et une bonne stabilité dimensionnelle. The applicant has unexpectedly discovered that the use of polyamide resin modified with hydroxyaromatic compounds for the manufacture of composite articles made it possible to obtain articles having not only good mechanical properties, such as in particular rigidity, breaking strength, impact resistance, and fatigue behavior, even when manufactured with shorter cycle times than those usually used, and without any other treatment, but also good resistance to hygrothermal aging. This makes it possible to provide a composite material which has both the advantage of reducing manufacturing costs, the use of tools implementing shortened cycle times, and also sufficient durability for structural applications. Composite articles according to the present invention also exhibit low water uptake and good dimensional stability.
Ces articles composites présentent notamment un très bon maintien des propriétés mécaniques après un vieillissement hygrothermique, notamment par rapport aux articles composites polyamides classiques. These composite articles have in particular a very good maintenance of mechanical properties after hygrothermal aging, particularly compared to conventional composite polyamide articles.
Les articles selon l'invention présentent notamment les avantages de rigidité, légèreté, et recyclabilité, et un bon aspect de surface. Ces articles présentent également de bonnes propriétés d'ignifugation. The articles according to the invention have in particular the advantages of rigidity, lightness, and recyclability, and a good surface appearance. These articles also have good fireproofing properties.
L'invention a pour premier objet un procédé de fabrication d'un article composite comprenant au moins : The invention firstly relates to a method of manufacturing a composite article comprising at least:
a) une étape d'imprégnation d'une étoffe de renfort avec une composition polyamide à l'état fondu, ledit polyamide comprend des motifs hydroxyaromatiques chimiquement liés à la chaîne du polyamide, la composition comprenant au moins une résine novolaque ; a) a step of impregnating a reinforcing fabric with a polyamide melt composition, said polyamide comprises hydroxyaromatic units chemically bonded to the polyamide chain, the composition comprising at least one novolac resin;
b) une étape de refroidissement et ensuite de récupération de l'article composite. b) a step of cooling and then recovering the composite article.
La présente invention concerne également un article composite comprenant au moins une étoffe de renfort et un polyamide modifié contenant des motifs hydroxyaromatiques chimiquement liés à la chaîne du polyamide, et une résine novolaque. The present invention also relates to a composite article comprising at least one reinforcing fabric and a modified polyamide containing patterns. hydroxyaromatic chemically bonded to the polyamide chain, and a novolac resin.
On entend par étoffe, une surface textile de fils ou de fibres éventuellement solidarisés par un procédé quelconque, tel que notamment collage, feutrage, tressage, tissage, tricotage. Ces étoffes sont aussi désignés comme des réseaux fibreux ou filamenteux. Par fil, on entend un monofilament, un fil multifilamentaire continu, un filé de fibres, obtenu à partir d'un unique type de fibres ou de plusieurs types de fibres en mélange intime. Le fil continu peut être également obtenu par assemblage de plusieurs fils multifilamentaires. Par fibre, on entend un filament ou un ensemble de filaments coupés, craqués ou convertis. By "fabric" is meant a textile surface of yarns or fibers possibly joined together by any method, such as, in particular, gluing, felting, braiding, weaving or knitting. These fabrics are also referred to as fibrous or filamentary networks. By wire is meant a monofilament, a continuous multifilament yarn, a spun yarn, obtained from a single type of fiber or several types of fibers in intimate mixture. The continuous wire can also be obtained by assembling several multifilament yarns. By fiber is meant a filament or a set of cut, cracked or converted filaments.
Les fils et/ou fibres de renfort selon l'invention sont préférentiellement choisis parmi les fils et/ou les fibres de carbone, de verre, d'aramides, de polyimides, de lin, de chanvre, de sisal, de coir, de jute, de kenaf et/ou de leur mélange. Plus préférentiellement, les étoffes de renfort sont uniquement constituées de fils et/ou fibres de renfort choisis parmi les fils et/ou les fibres de carbone, de verre, d'aramides, de polyimides, de lin, de chanvre, de sisal, de coir, de jute, de kenaf et/ou de leur mélange. The yarns and / or reinforcing fibers according to the invention are preferably chosen from yarns and / or fibers of carbon, glass, aramids, polyimides, flax, hemp, sisal, coir and jute. , kenaf and / or their mixture. More preferably, the reinforcement fabrics consist solely of yarns and / or reinforcing fibers chosen from among the yarns and / or the fibers of carbon, glass, aramids, polyimides, flax, hemp, sisal, coir, jute, kenaf and / or their mixture.
Ces étoffes on préférentiellement un grammage, c'est-à-dire le poids au mètre carré, compris entre 100 et 1000 g/m2. These fabrics are preferably a grammage, that is to say the weight per square meter, between 100 and 1000 g / m 2 .
Leur structure peut être aléatoire, unidirectionelle (1 D), ou multidirectionnelle (2D, 2,5D, 3D ou autre). Their structure can be random, unidirectional (1D), or multidirectional (2D, 2,5D, 3D or other).
Un article composite selon l'invention peut comprendre plusieurs étoffes de renfort de nature différente ou non. Les étoffes peuvent éventuellement être enduites ou ensimées, notamment pour apporter des fonctionnalités particulières. Le polyamide selon l'invention présente avantageusement une viscosité fondue η inférieure à 250 Pa.s, préférentiellement entre 1 et 50 Pa.s. Cette viscosité peut être mesurée à l'aide d'un rhéomètre plan-plan de diamètre 50 mm, sous un balayage en cisaillement par pallier allant de 1 à 160 s-1 . Le polymère est sous forme de film d'une épaisseur 150 μιτι, de granulés ou de poudre. Le polymère est amené à une température de 25 à 30°C au dessus de son point de fusion, et la mesure est alors effectuée. A composite article according to the invention may comprise several reinforcing fabrics of different nature or not. The fabrics may optionally be coated or sized, in particular to provide special features. The polyamide according to the invention advantageously has a melt viscosity η less than 250 Pa.s, preferably between 1 and 50 Pa.s. This viscosity can be measured using a planar planar rheometer with a diameter of 50 mm, under a shear streaking sweep ranging from 1 to 160 s-1. The polymer is in the form of a film with a thickness of 150 μιτι, granules or powder. The polymer is brought to a temperature of 25 to 30 ° C above its melting point, and the measurement is then carried out.
La masse moléculaire moyenne en nombre (Mn) des polyamides est préférentiellement supérieure à 6000 g/mol, plus préférentiellement compris entre 8000 g/mol et 20000 g/mol , ayant des propriétés mécaniques suffisantes et une certaine tenue lors des différents procédés de mises en forme. The number-average molecular weight (Mn) of the polyamides is preferably greater than 6000 g / mol, more preferably between 8000 g / mol and 20000 g / mol, having sufficient mechanical properties and a certain resistance during the various methods of setting up. form.
Les polyamides semi-cristallins sont particulièrement préférés. Semi-crystalline polyamides are particularly preferred.
La présente invention concerne notamment un polyamide modifié par un composé contenant au moins un groupement hydroxyle aromatique chimiquement lié à la chaîne polymère, ce polyamide pouvant être obtenu par polymérisation, outre les monomères du polyamide, d'un composé hydroxyaromatique ou par mélange en phase fondue d'un polyamide partiellement ou totalement formé avec un composé hydroxyaromatique, notamment lors d'une extrusion réactive. Le polyamide modifié selon l'invention peut également être obtenu par polycondensation en phase solide ou en phase solvant pour certains polyamides. The present invention relates in particular to a polyamide modified with a compound containing at least one aromatic hydroxyl group chemically bonded to the polymer chain, this polyamide being obtainable by polymerization, in addition to the monomers of the polyamide, of a hydroxyaromatic compound or by melt-phase mixing of a polyamide partially or totally formed with a hydroxyaromatic compound, in particular during a reactive extrusion. The modified polyamide according to the invention can also be obtained by solid phase polycondensation or solvent phase for certain polyamides.
Les monomères du polyamides peuvent notamment être des monomères diacides, notamment aliphatique, cycloaliphatique, arylaliphatique ou aromatique, des monomères diamines, notamment aliphatiques, et/ou des aminoacides ou lactames. Ce sont généralement les monomères classiquement utilisés pour la fabrication de polyamides semi-cristallins, tels que les polyamides aliphatiques, polyamides semi-aromatiques et plus généralement, les polyamides linéaires obtenus par polycondensation entre un diacide saturé aliphatique ou aromatique, et une diamine primaire saturée aromatique ou aliphatique, les polyamides obtenus par condensation d'un lactame, d'un aminoacide ou les polyamides linéaires obtenus par condensation d'un mélange de ces différents monomères. Plus précisément, ces copolyamides peuvent être, par exemple, le polyadipamide d'hexaméthylène, les polyphtalamides obtenus à partir d'acide téréphtalique et/ou isophtalique, les copolyamides obtenus à partir d'acide adipique, d'hexaméthylène diamine et de caprolactame. The monomers of the polyamides may in particular be diacid monomers, in particular aliphatic, cycloaliphatic, arylaliphatic or aromatic monomers, diamine monomers, in particular aliphatic monomers, and / or amino acids or lactams. These are generally the monomers conventionally used for the production of semi-crystalline polyamides, such as aliphatic polyamides, semi-aromatic polyamides and, more generally, linear polyamides obtained by polycondensation between a saturated diacid aliphatic or aromatic, and a primary saturated aromatic or aliphatic diamine, the polyamides obtained by condensation of a lactam, an amino acid or linear polyamides obtained by condensation of a mixture of these different monomers. More specifically, these copolyamides may be, for example, hexamethylene polyadipamide, polyphthalamides obtained from terephthalic and / or isophthalic acid, copolyamides obtained from adipic acid, hexamethylenediamine and caprolactam.
Les monomères des polyamides peuvent éventuellement contenir des insaturations ou des hétéroatomes tels l'oxygène, le soufre, l'azote. The monomers of the polyamides may optionally contain unsaturations or heteroatoms such as oxygen, sulfur or nitrogen.
On peut notamment utiliser les polyamides choisis dans le groupe comprenant le polyamide 6, le polyamide 66, le polyamide 6.10, le polyamide 1 1 , le polyamide 12, le polyamide 6.12, le poly(méta-xylylène adipamide) (MXD6), le polyamide 66/6T, le polyamide 66/61, les mélanges et copolyamides, tels que le copolyamide 6.66 par exemple. La composition de l'invention peut également comprendre les copolyamides dérivés notamment des polyamides ci-dessus, ou les mélanges de ces polyamides ou copolyamides. Les polyamides préférés sont le polyhexaméthylène adipamide, le polycaprolactame, ou les copolymères et mélanges entre le polyhexaméthylène adipamide et le polycaprolactame. In particular, the polyamides chosen from the group comprising polyamide 6, polyamide 66, polyamide 6.10, polyamide 11, polyamide 12, polyamide 6.12, poly (meta-xylylene adipamide) (MXD6), polyamide may be used. 66 / 6T, polyamide 66/61, blends and copolyamides, such as copolyamide 6.66 for example. The composition of the invention may also comprise copolyamides derived in particular from the above polyamides, or mixtures of these polyamides or copolyamides. The preferred polyamides are polyhexamethylene adipamide, polycaprolactam, or copolymers and blends between polyhexamethylene adipamide and polycaprolactam.
Les acides dicarboxyliques peuvent également être choisis parmi l'acide glutarique, l'acide adipique, l'acide pimellique, l'acide subérique, l'acide azélaïque, l'acide sébacique, l'acide dodécanedioïque ; l'acide 1 ,2-ou 1 ,3- cyclohexane dicarboxylique ; l'acide 1 ,2-ou 1 ,3-phénylène diacétique ; l'acide 1 ,2-ou 1 ,3-cylohexane diacétique ; l'acide isophthalique ; l'acide téréphthalique ; l'acide 4,4'-benzophénone dicarboxylique; l'acide 2,5-naphthalène dicarboxylique; et l'acide p-t-butyl isophthalique. L'acide dicarboxylique préféré est l'acide adipique. Les diamines peuvent par exemple être choisies parmi l'hexaméthylène diamine; la butane diamine ; la pentane diamine ; la 2-méthyl pentaméthylène diamine ; la 2-méthyl hexaméthylène diamine ; la 3-méthyl hexa-méthylène diamine ; la 2,5- diméthyl hexaméthylène diamine ; la 2,2-diméthylpentaméthylène diamine ; la nonane diamine ; la décanediamine ; la 5-méthylnonane diamine ; la dodécaméthylène diamine ; la 2,2,4-et 2,4,4-triméthyl hexaméthylène diamine ; la 2,2,7,7-tétraméthyl octaméthylène diamine ; l'isophorone diamine ; le diaminodicyclohexyl méthane et les diamines aliphatiques en C2 -C16 qui peuvent être substituées par un ou plusieurs groupements alkyles. La diamine préférée est l'hexaméthylène diamine. The dicarboxylic acids may also be chosen from glutaric acid, adipic acid, pimellic acid, suberic acid, azelaic acid, sebacic acid and dodecanedioic acid; 1,2-or 1,3-cyclohexane dicarboxylic acid; 1,2-or 1,3-phenylene diacetic acid; 1, 2-or 1,3-cyclohexane diacetic acid; isophthalic acid; terephthalic acid; 4,4'-benzophenone dicarboxylic acid; 2,5-naphthalene dicarboxylic acid; and pt-butyl isophthalic acid. The preferred dicarboxylic acid is adipic acid. The diamines may for example be chosen from hexamethylenediamine; butane diamine; pentane diamine; 2-methyl pentamethylene diamine; 2-methyl hexamethylenediamine; 3-methyl hexamethylene diamine; 2,5-dimethyl hexamethylenediamine; 2,2-dimethylpentamethylenediamine; nonane diamine; decanediamine; 5-methylnonanediamine; dodecamethylene diamine; 2,2,4- and 2,4,4-trimethyl hexamethylenediamine; 2,2,7,7-tetramethyl octamethylene diamine; isophorone diamine; diaminodicyclohexyl methane and C2-C16 aliphatic diamines which may be substituted by one or more alkyl groups. The preferred diamine is hexamethylenediamine.
Le polyamide modifié de l'invention peut être obtenu à partir notamment d'un monomère lactame ou un aminoacide, de préférence aliphatique. A titre d'exemple de tels lactames ou aminoacides, on peut citer le caprolactame, l'acide 6-aminohexanoïque, l'acide 5-aminopentanoïque, l'acide 7- aminoheptanoïque, l'acide 1 1 -aminoundécanoïque, le dodécanolactame. The modified polyamide of the invention can be obtained from, in particular, a lactam monomer or an amino acid, preferably an aliphatic one. By way of example of such lactams or amino acids, mention may be made of caprolactam, 6-aminohexanoic acid, 5-aminopentanoic acid, 7-aminoheptanoic acid, 11-aminoundecanoic acid and dodecanolactam.
Ces polyamides peuvent notamment être modifiés par des monomères difonctionnels ou monofonctionnels, tels que notamment des diacides ou diamines, monoacides ou monoamines. Des molécules polyfonctionnelles, au moins trifonctionnelles, peuvent également être utilisées pour apporter des ramifications ou branchements au polyamide. On citera par exemple la bishexaméthylènetriamine. Des polyamides selon l'invention peuvent aussi être obtenus par mélange, notamment en fondu, de polyamides avec des monomères modifiant la longueur des chaînes, tel que notamment des diamines, diacides carboxyliques, monoamines et/ou monoacides carboxyliques. La composition de l'invention peut également comprendre les copolyamides dérivés notamment des polyamides ci-dessus, ou les mélanges de ces polyamides ou (co)polyamides. On peut également utiliser comme polyamide de haute fluidité un polyamide étoile comprenant des chaînes macromoléculaires étoiles et le cas échéant des chaînes macromoléculaires linéaires. These polyamides may in particular be modified with difunctional or monofunctional monomers, such as especially diacids or diamines, monoacids or monoamines. Polyfunctional molecules, at least trifunctional, may also be used to provide branches or connections to the polyamide. For example, bishexamethylenetriamine is mentioned. Polyamides according to the invention may also be obtained by mixing, in particular melt, polyamides with chain length-changing monomers, such as in particular diamines, dicarboxylic acids, monoamines and / or mono carboxylic acids. The composition of the invention may also comprise copolyamides derived in particular from the above polyamides, or mixtures of these polyamides or (co) polyamides. It is also possible to use, as high-flow polyamide, a star polyamide comprising star macromolecular chains and, where appropriate, linear macromolecular chains.
Le polyamide à structure étoile est un polymère comprenant des chaînes macromoléculaires étoiles, et éventuellement des chaînes macromoléculaires linéaires, les polymères comprenant de telles chaînes macromoléculaires étoiles sont par exemple décrits dans les documents FR2743077, FR2779730, EP0682057 et EP0832149. Ces composés sont connus pour présenter une fluidité améliorée par rapport à des polyamides linéaires. The star-shaped polyamide is a polymer comprising star macromolecular chains, and optionally linear macromolecular chains, the polymers comprising such star macromolecular chains are for example described in the documents FR2743077, FR2779730, EP0682057 and EP0832149. These compounds are known to exhibit improved fluidity over linear polyamides.
Les chaînes macromoléculaires étoiles comportent un cœur et au moins trois branches de polyamide. Les branches sont liées au cœur par une liaison covalente, par l'intermédiaire d'un groupement amide ou d'un groupement d'une autre nature. Le cœur est un composé chimique organique ou organométallique, de préférence un composé hydrocarboné comportant éventuellement des hétéroatomes et auquel sont reliées les branches. Les branches sont des chaînes polyamides. Les chaînes polyamides constituant les branches sont de préférence du type de celles obtenues par polymérisation des lactames ou aminoacides, par exemple de type polyamide 6. The star macromolecular chains comprise a core and at least three branches of polyamide. The branches are linked to the heart by a covalent bond, via an amide group or a group of another nature. The core is an organic or organometallic chemical compound, preferably a hydrocarbon compound optionally comprising heteroatoms and to which the branches are connected. The branches are polyamide chains. The polyamide chains constituting the branches are preferably of the type obtained by polymerization of lactams or amino acids, for example of the polyamide 6 type.
Le polyamide à structure étoile selon l'invention comprend éventuellement, outre les chaînes étoiles, des chaînes polyamide linéaires. Dans ce cas, le rapport en poids entre la quantité de chaînes étoiles et la somme des quantités de chaînes étoiles et de chaînes linéaires est compris entre 0,5 et 1 bornes incluses. Il est de préférence compris entre 0,6 et 0,9. The polyamide star structure according to the invention optionally comprises, in addition to star chains, linear polyamide chains. In this case, the ratio by weight between the quantity of star chains and the sum of the quantities of star and linear chains is between 0.5 and 1 inclusive. It is preferably between 0.6 and 0.9.
Par acide carboxylique, on entend les acides carboxyliques et leurs dérivés, tels que les anhydrides d'acide, les chlorures d'acide, les amides ou les esters. Des procédés d'obtention de ces polyamides étoiles sont décrits dans les documents FR2743077 et FR2779730. Ces procédés conduisent à la formation de chaînes macromoléculaires étoiles, en mélange avec éventuellement des chaînes macromoléculaires linéaires. The term "carboxylic acid" means carboxylic acids and their derivatives, such as acid anhydrides, acid chlorides, amides or esters. Processes for obtaining these star polyamides are described in documents FR2743077 and FR2779730. These processes lead to the formation of star macromolecular chains, in mixture with possibly linear macromolecular chains.
La composition selon l'invention présente préférentiellement de 30 à 75 % en volume de polyamide, par rapport au poids total de la composition, préférentiellement de 35 à 60 % en volume. Le composé hydroxyaromatique est un composé portant au moins une, notamment une ou deux, fonctions capables de réagir avec les fonctions aminés ou acides du polyamide ou des monomères du polyamide. The composition according to the invention preferably has from 30 to 75% by volume of polyamide, relative to the total weight of the composition, preferably from 35 to 60% by volume. The hydroxyaromatic compound is a compound carrying at least one, in particular one or two, functions capable of reacting with the amine or acid functional groups of the polyamide or of the monomers of the polyamide.
Par « groupement hydroxyle aromatique », on entend une fonction hydroxyle rattachée à un atome de carbone faisant partie d'un cycle aromatique. By "aromatic hydroxyl group" is meant a hydroxyl function attached to a carbon atom forming part of an aromatic ring.
Par « composé hydroxyaromatique », on entend un composé organique comportant au moins un groupement hydroxyle aromatique. Par « chimiquement lié » on entend lié par une liaison covalente. Une fois chimiquement lié à la chaîne polyamide, le composé hydroxyaromatique devient un motif hydroxyaromatique et le polyamide modifié de l'invention est un polyamide contenant des motifs hydroxyaromatiques. Les fonctions du composé hydroxyaromatique pouvant réagir avec les fonctions du polyamide sont notamment les fonctions acide, cétone, aminé et aldéhyde. By "hydroxyaromatic compound" is meant an organic compound having at least one aromatic hydroxyl group. By "chemically linked" is meant bound by a covalent bond. Once chemically bonded to the polyamide chain, the hydroxyaromatic compound becomes a hydroxyaromatic unit and the modified polyamide of the invention is a polyamide containing hydroxyaromatic units. The functions of the hydroxyaromatic compound that can react with the functions of the polyamide include the acid, ketone, amine and aldehyde functions.
Par « fonction acide » on entend une fonction acide carboxylique ou dérivée, telles que chlorure d'acide, anhydride d'acide, amide, ester. By "acid function" is meant a carboxylic acid or derivative function, such as acid chloride, acid anhydride, amide, ester.
Les groupements hydroxyle aromatique de l'invention ne sont pas considérés comme des fonctions réagissant avec les fonctions acide. Avantageusement le groupement hydroxyle du monomère n'est pas encombré, c'est-à-dire par exemple que les atomes de carbone situés en a de la fonction hydroxyle ne sont de préférence pas substitués par des substituants encombrants, tels que des alkyles ramifiés. The aromatic hydroxyl groups of the invention are not considered to be functions reactive with acid functions. Advantageously, the hydroxyl group of the monomer is not congested, that is to say for example that the carbon atoms located at a of the hydroxyl function are preferably not substituted by bulky substituents, such as branched alkyls.
Le composé hydroxyaromatique peut par exemple être représenté par la formule suivante (I) : The hydroxyaromatic compound may for example be represented by the following formula (I):
(HO)x-Z-(F)n (I) (HO) x -Z- (F) n (I)
dans laquelle : in which :
- Z est un radical hydrocarboné aromatique ou arylaliphatique multivalent (au moins divalent), Z is a multivalent aromatic or arylaliphatic hydrocarbon radical (at least divalent),
x est compris entre 1 et 10 ;  x is from 1 to 10;
F est une fonction acide, aldéhyde, aminé, cétone capable de se lier à une fonction acide ou aminé des monomères du polyamide, et  F is an acid, aldehyde, amine, ketone function capable of binding to an acid or amine function of the monomers of the polyamide, and
- n est compris entre 1 et 5. n is between 1 and 5.
Z peut par exemple être choisi dans le groupe comprenant : le benzène, le méthyle benzène, le naphtalène, le biphényle, le diphényle éther, le diphényle sulfure, le diphényle sulfone, le ditolyle éther, le xylylène, le diéthyl benzène, ou la pyridine. Z may for example be selected from the group consisting of: benzene, methyl benzene, naphthalene, biphenyl, diphenyl ether, diphenyl sulfide, diphenyl sulfone, ditolyl ether, xylylene, diethyl benzene, or pyridine .
Par « radical arylaliphatique » on entend un radical selon lequel au moins une fonction F du composé de formule (I) n'est pas rattachée à ce radical par un atome de carbone faisant partie d'un cycle aromatique. By "arylaliphatic radical" is meant a radical according to which at least one F function of the compound of formula (I) is not attached to this radical by a carbon atom forming part of an aromatic ring.
Avantageusement Z comporte entre 6 et 18 atomes de carbone. Advantageously Z has between 6 and 18 carbon atoms.
Un composé hydroxyaromatique peut parfaitement contenir plusieurs types de fonctions F de nature différente. A hydroxyaromatic compound can perfectly contain several types of F functions of different nature.
Ce composé est de préférence choisi dans le groupe comprenant : l'acide 2- hydroxytéréphtalique, l'acide 5-hydroxyisophtalique, l'acide 4- hydroxyisophtalique, l'acide 2,5-dihydroxytéréphtalique, l'acide 4- hydroxyphénylacétique ou l'acide gallique, la L-Tyrosine, l'acide 4- hydroxyphénylacétique, le 3,5-diaminophénol, le 5-hydroxy m-xylylène diamine, l'annino-3 phénol, l'amino-3 méthyl-4 phénol, et l'acide hydroxy-3 amino-5 benzoïque. This compound is preferably selected from the group consisting of: 2-hydroxyterephthalic acid, 5-hydroxyisophthalic acid, 4- hydroxyisophthalic acid, 2,5-dihydroxyterephthalic acid, 4-hydroxyphenylacetic acid or gallic acid, L-Tyrosine, 4-hydroxyphenylacetic acid, 3,5-diaminophenol, 5-hydroxy-m-xylylene diamine 3-Anninophenol, 3-amino-4-methylphenol, and 3-hydroxy-5-amino benzoic acid.
Dans le cadre de l'invention, des mélanges de différents composés de formule (I) peuvent être mis en œuvre. La proportion molaire de composé hydroxyaromatique par rapport à l'ensemble des monomères constituants le polyamide, par exemple la somme des monomères diacide, diamine, aminoacides et le composé hydroxyaromatique, est généralement comprise entre 0,1 et 100 %, préférentiellement entre 1 et 70 %, plus préférentiellement entre 0,5 et 60 %, encore plus préférentiellement comprise entre 2,5 et 50 %. In the context of the invention, mixtures of different compounds of formula (I) may be used. The molar proportion of hydroxyaromatic compound relative to all the monomers constituting the polyamide, for example the sum of the diacid, diamine, amino acid monomers and the hydroxyaromatic compound, is generally between 0.1 and 100%, preferably between 1 and 70. %, more preferably between 0.5 and 60%, more preferably between 2.5 and 50%.
Le polyamide de l'invention est notamment obtenu par un procédé de polymérisation à l'état fondu des différents monomères décrits ci-dessus, ces monomères étant présents en totalité ou en partie. The polyamide of the invention is especially obtained by a melt polymerization process of the various monomers described above, these monomers being present in whole or in part.
Par l'expression « polymérisation à l'état fondu » on entend que la polymérisation est réalisée à l'état liquide, et que le milieu de polymérisation ne contient pas de solvant autre que de l'eau, éventuellement. Le milieu de polymérisation peut par exemple être une solution aqueuse comprenant les monomères, ou un liquide comprenant les monomères. Avantageusement le milieu de polymérisation comprend de l'eau comme solvant. Cela facilite l'agitation du milieu, et donc son homogénéité. Le milieu de polymérisation peut également comprendre des additifs tels que des limiteurs de chaîne. Le polyamide modifié de l'invention est généralement obtenu par polycondensation entre les différents monomères, présents en totalité ou en partie, pour former des chaînes polyamides, avec formation du produit d'élimination, en particulier l'eau, dont une partie peut se vaporiser. Le polyamide modifié de l'invention est généralement obtenu, par chauffage à température et pression élevées, par exemple d'une solution aqueuse comprenant les monomères, ou d'un liquide comprenant les monomères, pour évaporer le produit d'élimination, en particulier l'eau (présente initialement dans le milieu de polymérisation et/ou formée lors de la polycondensation) tout en évitant toute formation de phase solide afin d'éviter une prise en masse. By the term "melt polymerization" it is meant that the polymerization is carried out in the liquid state, and that the polymerization medium contains no solvent other than water, possibly. The polymerization medium may for example be an aqueous solution comprising the monomers, or a liquid comprising the monomers. Advantageously, the polymerization medium comprises water as a solvent. This facilitates the agitation of the medium, and therefore its homogeneity. The polymerization medium may also include additives such as chain limiters. The modified polyamide of the invention is generally obtained by polycondensation between the various monomers, present in whole or in part, to form polyamide chains, with formation of the elimination product, in particular water, a part of which can vaporize . The modified polyamide of the invention is generally obtained by heating at high temperature and pressure, for example an aqueous solution comprising the monomers, or a liquid comprising the monomers, to evaporate the elimination product, in particular water (initially present in the polymerization medium and / or or formed during the polycondensation) while avoiding any formation of solid phase to avoid caking.
La réaction de polycondensation est généralement effectuée à une pression d'environ 0,5-3,5 MPa (0,5-2,5 MPa) à une température d'environ 100-320°C (180- 300°C). La polycondensation est généralement poursuivie en phase fondue à pression atmosphérique ou réduite de manière à atteindre le degré d'avancement souhaité. The polycondensation reaction is generally carried out at a pressure of about 0.5-3.5 MPa (0.5-2.5 MPa) at a temperature of about 100-320 ° C (180-300 ° C). The polycondensation is generally continued in the melt phase at atmospheric pressure or reduced so as to reach the desired degree of advancement.
Le produit de polycondensation est un polymère ou prépolymère fondu. Il peut comprendre une phase vapeur essentiellement constituée de vapeur du produit d'élimination, en particulier d'eau, susceptible d'avoir été formée et/ou vaporisée. The polycondensation product is a molten polymer or prepolymer. It may comprise a vapor phase consisting essentially of vapor of the elimination product, in particular water, which may have been formed and / or vaporized.
Ce produit peut être soumis à des étapes de séparation de phase vapeur et de finition afin d'atteindre le degré de polycondensation désiré. La séparation de la phase vapeur peut par exemple être réalisée dans un dispositif de type cyclone. De tels dispositifs sont connus. This product can be subjected to vapor phase separation and finishing steps to achieve the desired degree of polycondensation. The separation of the vapor phase may for example be carried out in a cyclone device. Such devices are known.
La finition consiste à maintenir le produit de polycondensation à l'état fondu, sous une pression voisine de la pression atmosphérique ou sous pression réduite, pendant un temps suffisant pour atteindre le degré d'avancement désiré. Une telle opération est connue de l'homme du métier. La température de l'étape de finition est avantageusement supérieure ou égale à 100°C et dans tous les cas supérieure à la température de solidification du polymère. Le temps de séjour dans le dispositif de finition est de préférence supérieur ou égal à 5 minutes. Le produit de polycondensation peut également subir une étape de postcondensation en phase solide. Cette étape est connue de l'homme du métier et permet d'augmenter le degré de polycondensation à une valeur souhaitée. Le procédé de l'invention est similaire dans ses conditions au procédé classique de préparation de polyamide du type de ceux obtenus à partir d'acides dicarboxyliques et de diamines, en particulier du procédé de fabrication de polyamide 66 à partir d'acide adipique et d'hexaméthylène diamine. Ce procédé de fabrication de polyamide 66 est connu de l'homme du métier. Le procédé de fabrication de polyamide du type de ceux obtenus à partir d'acides dicarboxyliques et de diamines utilise généralement comme matière première, un sel obtenu par un mélange en quantité stoechiométrique en général dans un solvant comme l'eau, d'un diacide avec une diamine. Ainsi, dans la fabrication du poly(hexaméthylène adipamide), l'acide adipique est mélangé avec de l'hexaméthylène diamine généralement dans de l'eau pour obtenir de l'adipate d'hexaméthylène diammonium plus connu sous le nom de sel Nylon ou "Sel N". Ainsi, lorsque le procédé de l'invention met en œuvre un diacide et une diamine, ces composés peuvent être introduits, au moins en partie, sous la forme d'un sel. En particulier lorsque le diacide est l'acide adipique et la diamine l'hexaméthylène diamine, ces composés peuvent être introduits au moins en partie sous forme de sel N. Ceci permet d'avoir un équilibre stœchiométrique. De même lorsque le composé hydroxyaromatique est un diacide ou une diamine, il est également possible de l'introduire sous forme de sels, avec une diamine ou un diacide. The finish consists in maintaining the polycondensation product in the molten state, at a pressure close to atmospheric pressure or under reduced pressure, for a time sufficient to reach the desired degree of advancement. Such an operation is known to those skilled in the art. The temperature of the finishing step is advantageously greater than or equal to 100 ° C. and in all cases greater than the solidification temperature of the polymer. The residence time in the finishing device is preferably greater than or equal to 5 minutes. The polycondensation product can also undergo a solid phase postcondensation step. This step is known to those skilled in the art and makes it possible to increase the degree of polycondensation to a desired value. The process of the invention is similar in its conditions to the conventional method for preparing polyamide of the type of those obtained from dicarboxylic acids and diamines, in particular the process for producing polyamide 66 from adipic acid and from hexamethylene diamine. This method of manufacturing polyamide 66 is known to those skilled in the art. The process for producing polyamide of the type of those obtained from dicarboxylic acids and diamines generally uses as raw material, a salt obtained by a mixture in stoichiometric quantity, generally in a solvent such as water, a diacid with a diamine. Thus, in the manufacture of poly (hexamethylene adipamide), adipic acid is mixed with hexamethylene diamine generally in water to obtain hexamethylene diammonium adipate better known as nylon salt or " Salt N ". Thus, when the process of the invention uses a diacid and a diamine, these compounds can be introduced, at least in part, in the form of a salt. In particular when the diacid is adipic acid and diamine hexamethylenediamine, these compounds can be introduced at least partly in the form of N salt. This makes it possible to have a stoichiometric equilibrium. Likewise, when the hydroxyaromatic compound is a diacid or a diamine, it is also possible to introduce it in the form of salts, with a diamine or a diacid.
Le procédé de l'invention conduit généralement à un polymère statistique lorsque le composé hydroxyaromatique est polyfonctionnel, notamment au moins difonctionnel, et à un polyamide ayant partiellement ou totalement des terminaisons hydroxyaromatique, lorsque le composé hydroxyaromatique est monofonctionnel. The process of the invention generally leads to a random polymer when the hydroxyaromatic compound is polyfunctional, especially at least difunctional, and to a polyamide having partially or completely hydroxyaromatic terminations, when the hydroxyaromatic compound is monofunctional.
Le polyamide modifié obtenu à la fin de l'étape de finition peut être refroidi et mis sous forme de granulés. Le polyamide modifié obtenu par le procédé de l'invention sous forme fondue peut être directement mis en forme ou être extrudé et granulé, pour une mise en forme ultérieure après fusion. Le polyamide modifié selon l'invention peut être utilisé en tant que matrice, seul ou en combinaison avec d'autres polymères thermoplastiques, notamment des polyamides, polyesters, ou polyoléfines. The modified polyamide obtained at the end of the finishing step can be cooled and granulated. The modified polyamide obtained by the process of the invention in molten form can be directly shaped or extruded and granulated, for subsequent shaping after melting. The modified polyamide according to the invention can be used as a matrix, alone or in combination with other thermoplastic polymers, in particular polyamides, polyesters, or polyolefins.
La composition polyamide selon l'invention est notamment utilisée en tant que matrice, notamment par granulation, calandrage, extrusion sous forme de film, broyage, injection, moulage, moulage par injection, pressage, et autres. The polyamide composition according to the invention is especially used as a matrix, in particular by granulation, calendering, extrusion in the form of a film, grinding, injection, molding, injection molding, pressing, and others.
L'étape d'imprégnation de la composition polyamide de l'invention et de l'étoffe de renfort peut être réalisée de diverses manières, selon divers procédés possibles. II est parfaitement possible de procéder à l'imprégnation d'une ou plusieurs étoffe de renfort. The impregnation step of the polyamide composition of the invention and the reinforcing fabric can be carried out in various ways, according to various possible methods. It is perfectly possible to impregnate one or more reinforcing fabric.
On peut par exemple injecter la composition polyamide en fondu dans une chambre de moulage comprenant au moins une ou plusieurs étoffes de renfort. L'intérieur de la chambre de moulage est à une température de plus ou moins 50°C par rapport à la température de fusion dudit polyamide. On peut procéder ensuite au refroidissement de la chambre de moulage et de l'article obtenu, pour enfin récupérer ledit article. Ce procédé est connu également sous le nom de procédé de moulage par transfert de résine (RTM) en procédé thermodur, qui consiste à injecter de la résine dans un moule fermé dans lequel ont été préalablement placées des fibres de renforcement. Ce procédé peut être réalisé sous pression. For example, the melt polyamide composition may be injected into a molding chamber comprising at least one or more reinforcing fabrics. The inside of the molding chamber is at a temperature of plus or minus 50 ° C with respect to the melting temperature of said polyamide. It is then possible to cool the molding chamber and the article obtained to finally recover said article. This process is also known as the thermoset resin transfer molding process (RTM), which consists in injecting resin into a closed mold in which reinforcement fibers have been previously placed. This process can be carried out under pressure.
On peut également réaliser un article composite selon l'invention par un procédé de « film stacking » qui consiste en une compression en température d'un empilement d'étoffes de renfort et de films de polyamide. On procède notamment à la mise en contact d'une ou plusieurs étoffes de renfort et un ou plusieurs films de polyamide modifiées par des composés hydroxyaromatiques et imprégnation des étoffes par fusion du polyamide. Les pressions nécessaires pour un bon assemblage, sont généralement supérieures à 30 bar. L'article composite selon l'invention peut aussi être réalisé par mise en contact d'une ou plusieurs étoffes de renfort avec de la poudre d'un polyamide tel que défini précédemment, notamment de la poudre fine, et l'on réalise ladite imprégnation par fusion du polyamide, à une température égale ou supérieure à celle du point de fusion du polyamide, éventuellement sous pression. It is also possible to produce a composite article according to the invention by a "film stacking" method which consists in a temperature compression of a stack of reinforcement fabrics and polyamide films. In particular, one or more reinforcing fabrics and one or more films are brought into contact with one another. of polyamide modified with hydroxyaromatic compounds and impregnation of the fabrics by melting the polyamide. The necessary pressures for a good assembly, are generally higher than 30 bar. The composite article according to the invention may also be produced by bringing one or more reinforcing fabrics into contact with the powder of a polyamide as defined above, in particular of the fine powder, and the said impregnation is carried out. by melting the polyamide at a temperature equal to or greater than that of the melting point of the polyamide, optionally under pressure.
L'article composite de l'invention peut également être réalisé par pultrusion. Cette technique consiste généralement à tirer à travers une filière chauffée un ou plusieurs fils et fibres continus de façon à l'imprégner d'une résine thermoplastique fondue pour obtenir un jonc ou article fini ou semi-fini. The composite article of the invention can also be made by pultrusion. This technique generally involves drawing through a heated die one or more continuous yarns and fibers so as to impregnate it with a molten thermoplastic resin to obtain a rod or finished or semi-finished article.
Après l'imprégnation de l'étoffe de renfort par le polyamide, l'article est obtenu par solidification de la matrice. Le refroidissement peut avantageusement être effectué rapidement de façon à éviter une cristallisation importante du polyamide, notamment pour maintenir les propriétés de l'article. Le refroidissement peut notamment être effectué en moins de 5 minutes, plus préférentiellement en moins d'une minute. Le moule peut par exemple être refroidit par un circuit de fluide froid. On peut aussi éventuellement transférer l'article composite dans un moule froid, éventuellement sous pression. La composition polyamide et/ou l'article composite selon l'invention peuvent également comprendre tous les additifs habituellement utilisés dans les compositions à base de polyamide utilisées pour la fabrication d'articles. Ainsi, on peut citer à titre d'exemple d'additifs les stabilisants thermiques, stabilisants UV, antioxydants, lubrifiants, les pigments, colorants, plastifiants, charges de renfort, agents modifiant la résistance aux chocs, et agents de couplage. Des additifs pour améliorer la qualité des interfaces étoffes de renfort polyamide peuvent également être utilisés. Ces additifs peuvent être par exemple incorporés à la composition polyamide, incorporés dans les fils et/ou fibres de l'étoffe de renfort, présents sur les fils et/ou fibres de ladite étoffe, ou encore déposés sur l'étoffe de renfort. Ces additifs peuvent être des agents de couplage tels que ceux de type aminosilanes ou chlorosilanes, ou encore des agents fluidifiants ou mouillants, ou leur association. After impregnation of the reinforcing fabric with the polyamide, the article is obtained by solidification of the matrix. The cooling can advantageously be carried out rapidly so as to avoid significant crystallization of the polyamide, in particular to maintain the properties of the article. The cooling can in particular be carried out in less than 5 minutes, more preferably in less than one minute. The mold may for example be cooled by a cold fluid circuit. It is also possible to transfer the composite article to a cold mold, possibly under pressure. The polyamide composition and / or the composite article according to the invention may also comprise all the additives normally used in polyamide-based compositions used for the manufacture of articles. Thus, examples of additives include thermal stabilizers, UV stabilizers, antioxidants, lubricants, pigments, dyes, plasticizers, reinforcing fillers, impact modifiers, and coupling agents. Additives to improve the quality of the polyamide reinforcing fabric interfaces can also be used. These additives may for example be incorporated into the polyamide composition, incorporated into the threads and / or fibers of the reinforcing fabric, present on the threads and / or fibers of said fabric, or else deposited on the reinforcing fabric. These additives may be coupling agents such as those of aminosilane or chlorosilane type, or fluidizing or wetting agents, or their combination.
Des charges renforçantes peuvent être incorporées à la composition polyamide. Ces charges peuvent être choisies parmi les charges fibreuses, tels que des fibres de verre courtes par exemple, ou des charges non fibreuses tels que le kaolin, le talc, la silice, le mica ou la wollastonite. Leur taille est généralement comprise entre 1 et 25 μιτι. Des charges sub-microniques voire nanométriques peuvent également être utilisées, seules ou en complément des autres charges. Reinforcing fillers may be incorporated in the polyamide composition. These fillers may be chosen from fibrous fillers, such as short glass fibers, for example, or non-fibrous fillers such as kaolin, talc, silica, mica or wollastonite. Their size is generally between 1 and 25 μιτι. Sub-micron or even nanometric charges may also be used, alone or in addition to other charges.
La composition polyamide comprend une résine novolaque. Elle peut comprendre une ou plusieurs types de résine novolaque différentes. The polyamide composition comprises a novolac resin. It may comprise one or more types of different novolac resin.
On entend généralement par résine novolaque, une résine phénolique dont le rapport formaldéhyde/phénol est inférieur à 1 et qui, de ce fait, reste normalement thermoplastique jusqu'à ce qu'elle soit chauffée avec une quantité appropriée d'un composé, par exemple formaldéhyde ou hexaméthylènetétramine, susceptible de donner des liaisons supplémentaires, par conséquent de donner un produit infusible. The term novolac resin is generally understood to mean a phenolic resin whose formaldehyde / phenol ratio is less than 1 and which therefore remains normally thermoplastic until it is heated with an appropriate quantity of a compound, for example formaldehyde or hexamethylenetetramine, which may give additional bonds, thus giving an infusible product.
Les résines novolaques généralement des produits de condensation de composés phénoliques avec des aldéhydes ou cétones. Ces réactions de condensation sont généralement catalysées par un acide ou une base. Les résines novolaques présentent généralement un degré de condensation compris entre 2 et 15. Novolak resins are generally condensation products of phenolic compounds with aldehydes or ketones. These condensation reactions are generally catalyzed by an acid or a base. The novolak resins generally have a degree of condensation of between 2 and 15.
Les composés phénoliques peuvent être choisis seuls ou en mélange parmi le phénol, le crésol, le xylénol, le naphtol, les alkylphénols, comme le butyl-phénol, le terbutyl-phénol, l'isooctyl-phénol, le nitrophénol, le phénylphénol, le résorcinol ou le biphénol A ; ou tout autre phénol substitué. The phenolic compounds can be chosen alone or as a mixture from phenol, cresol, xylenol, naphthol, alkylphenols, such as butyl phenol, terbutylphenol, isooctylphenol, nitrophenol, phenylphenol, resorcinol or biphenol A; or any other substituted phenol.
L'aldéhyde le plus fréquemment utilisé est le formaldéhyde. On peut toutefois en utiliser d'autres, tels que l'acétaldéhyde, le para-formaldéhyde, le butyraldéhyde, le crotonaldéhyde, le glyoxal, et le furfural. Comme cétone, on peut utiliser l'acétone, la méthyle éthyle cétone ou l'acétophénone. L'aldéhyde et/ou la cétone peuvent éventuellement porter un autre groupement fonctionnel, tel que par exemple une fonction acide carboxylique. On peut notamment citer à cet effet l'acide glyoxylique ou l'acide lévulinique. The most frequently used aldehyde is formaldehyde. However, others may be used, such as acetaldehyde, paraformaldehyde, butyraldehyde, crotonaldehyde, glyoxal, and furfural. As ketone, it is possible to use acetone, methyl ethyl ketone or acetophenone. The aldehyde and / or the ketone may optionally carry another functional group, such as, for example, a carboxylic acid function. For example, glyoxylic acid or levulinic acid may be mentioned.
Selon un mode de réalisation particulier de l'invention, la résine novolaque est un produit de condensation du phénol et du formaldéhyde. Les résines novolaques utilisées ont avantageusement un poids moléculaire compris entre 500 et 3000 g/mol, de préférence entre 800 et 2000 g/mol. According to a particular embodiment of the invention, the novolak resin is a condensation product of phenol and formaldehyde. The novolak resins used advantageously have a molecular weight of between 500 and 3000 g / mol, preferably between 800 and 2000 g / mol.
Comme résine novolaque commerciale, on peut citer notamment les produits commerciaux Durez®, Vulkadur® ou Rhenosin®. As commercial novolac resin, mention may be made in particular of Durez®, Vulkadur® or Rhenosin® commercial products.
La composition selon l'invention peut comprendre entre 1 à 20 % en poids de résine novolaque, notamment de 1 à 10 % en poids, par rapport au poids total de la composition. La présente invention concerne un article susceptible d'être obtenu par le procédé de l'invention. L'article peut notamment être un article composite à base de polyamide comprenant une étoffe de renfort, dans lequel le polyamide présente une viscosité fondue η comprise entre 1 et 50 Pa.s. Les articles selon l'invention comprennent préférentiellement entre 25 et 80 % en volume d'étoffe de renfort par rapport au poids total. Les articles de l'invention peuvent être des articles finis, ou semi-finis pouvant aussi être appelé pré-imprégnés. On peut par exemple procéder au thermoformage des articles composites sous forme de plaques pour leur donner une forme définie après refroidissement. L'invention concerne ainsi des articles composites ou préformes susceptibles d'être obtenus par le procédé selon la présente invention. The composition according to the invention may comprise from 1 to 20% by weight of novolac resin, especially from 1 to 10% by weight, relative to the total weight of the composition. The present invention relates to an article obtainable by the method of the invention. The article may in particular be a polyamide-based composite article comprising a reinforcing fabric, in which the polyamide has a melt viscosity η of between 1 and 50 Pa.s. The articles according to the invention preferably comprise between 25 and 80% by volume of reinforcing fabric with respect to the total weight. The articles of the invention may be finished or semi-finished articles which may also be called prepregs. For example, it is possible to thermoform composite articles in the form of plates to give them a defined shape after cooling. The invention thus relates to composite articles or preforms that can be obtained by the method according to the present invention.
Les articles de l'invention peuvent aussi être des structures de type sandwich présentant une âme insérée entre deux peaux. Les composites de l'invention peuvent être utilisés pour former les couches externes, en les associant à une âme type nid d'abeille ou type mousse. Les couches peuvent être assemblées par collage chimique ou thermique. The articles of the invention may also be sandwich type structures having a core inserted between two skins. The composites of the invention can be used to form the outer layers, by associating them with a core type honeycomb or foam type. The layers can be assembled by chemical or thermal bonding.
Les structures composites selon l'invention peuvent être employées dans de nombreux domaines tels que l'aéronautique, l'automobile, l'énergie, l'industrie électrique, l'industrie des sports et loisirs. Ces structures peuvent être utilisées pour réaliser des articles de sports tels que des skis ou bien pour réaliser des surfaces diverses telles que des planchers spéciaux, des cloisons, des carrosseries de véhicules, ou des panneaux publicitaires. Dans l'aéronautique ces structures sont utilisées notamment au niveau des carénages (fuselage, aile, empennage). Dans l'automobile, elles sont utilisées par exemple au niveau des planchers, des supports tels que les tablettes arrières, ou encore au niveau de pièces de structure. Un langage spécifique est utilisé 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 ce langage spécifique. Des modifications, améliorations et perfectionnements peuvent notamment être envisagés par une personne au fait du domaine technique concerné sur la base de ses propres connaissances générales. Le terme et/ou inclut les significations et, ou, ainsi que toutes les autres combinaisons possibles des éléments connectés à ce terme. Composite structures according to the invention can be used in many fields such as aeronautics, automotive, energy, electrical industry, sports and leisure industry. These structures can be used to make sports articles such as skis or to achieve various surfaces such as special floors, partitions, vehicle bodies, or billboards. In aeronautics these structures are used in particular at fairings (fuselage, wing, empennage). In the automobile, they are used for example at floors, supports such as rear shelves, or at the level of structural parts. A specific language is used in the description so as to facilitate understanding of the principle of the invention. It should nevertheless be understood that no limitation of the scope of the invention is envisaged by the use of this specific language. In particular, modifications, improvements and improvements may be considered by a person familiar with the technical field concerned on the basis of his own general knowledge. 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 vu des exemples donnés ci-dessous uniquement à titre indicatif. Other details or advantages of the invention will emerge more clearly in the light of the examples given below solely for information purposes.
PARTIE EXPERIMENTALE EXPERIMENTAL PART
Teneurs en groupements terminaux acide (GTC) et aminé (GTA) : dosées par potentiométrie, exprimées en meq/kg. Les teneurs en groupements terminaux phénol GTP (pour les composés hydroxyaromatiques monofonctionnels) sont déterminés à partir des quantités initiales de réactifs introduits dans le réacteur de synthèse.  Acid end group (GTC) and amine (GTA) endpoints: assayed by potentiometry, expressed in meq / kg. The phenol GTP terminal group contents (for the monofunctional hydroxyaromatic compounds) are determined from the initial amounts of reagents introduced into the synthesis reactor.
Masse molaire moyenne en nombre déterminée par la formule Mn=2.106/(GTA+GTC+GTP) et exprimées en g/mol. Molar mass in number determined by the formula Mn = 2.10 6 / (GTA + GTC + GTP) and expressed in g / mol.
Température de fusion (Tf) et enthalpie associée (ΔΗί), température de cristallisation au refroidissement (Tc) : déterminées par calorimétrie différentielle à balayage (DSC « Differential Scanning Calorimetry »), à l'aide d'un appareil Perkin Elmer Pyris 1 , à une vitesse de 10°C/min. Melting temperature (T f ) and associated enthalpy (ΔΗί), cooling crystallization temperature (T c ): determined by Differential Scanning Calorimetry (DSC), using a Perkin Elmer Pyris device 1, at a rate of 10 ° C / min.
Température de transition vitreuse (Tg) déterminées sur le même appareil à une vitesse de 40 °C/min. Ces polyamides ont été caractérisés par des mesures de viscosité à l'état fondu réalisés sur un rhéomètre plan-plan Ares (Rheometrics), à 280°C. Les courbes de viscosité en fonction du taux de cisaillement montrent que les polymères considérés ont un comportement Newtonien dans la gamme de taux de cisaillement compris entre 1 et 150 s-1 : la viscosité retenue est la valeur au plateau (entre 1 et 150 s-1 ). Les renforts utilisés dans les exemples sont sous forme de préformes en tissus de verre, coupés aux dimensions requises pour la fabrication des plaques c'est-à- dire 150 x 150 mm ou 200x300 mm. L'étoffe de renfort utilisée est un tissu en fibre de verre (0°-90°) d'origine Synteen & Luckenhaus issu d'un roving de 1200 tex, présentant un grammage de 600 g/m2. Glass transition temperature (T g ) determined on the same apparatus at a rate of 40 ° C / min. These polyamides were characterized by melt viscosity measurements made on an Ares (Rheometrics) plane-plane rheometer at 280 ° C. The viscosity curves as a function of the shear rate show that the polymers under consideration have a Newtonian behavior in the shear rate range between 1 and 150 s-1: the viscosity retained is the plateau value (between 1 and 150 s -1). 1). The reinforcements used in the examples are in the form of glass fabric preforms, cut to the dimensions required for the manufacture of the plates, that is to say 150 × 150 mm or 200 × 300 mm. The reinforcing fabric used is a fiberglass fabric (0 ° -90 °) of Synteen & Luckenhaus origin from a roving of 1200 tex, having a basis weight of 600 g / m 2 .
Le polyamide comparatif C1 utilisé dans les exemples est un polyamide 6.6 haute fluidité ayant un indice de viscosité IV de 97 mL/g, une viscosité fondue η de 30 Pa.s et un Mn de 1 1200 g/mol. The comparative polyamide C1 used in the examples is a high fluidity polyamide 6.6 having an IV viscosity index of 97 mL / g, a melt viscosity η of 30 Pa.s and a Mn of 1100 g / mol.
Exemple 1 : préparation d'un copolyamide PA 66/6HIA 95/5 molaire ou 94,2/5,8 en poids EXAMPLE 1 Preparation of a Copolyamide PA 66 / 6HIA 95/5 Molar or 94.2 / 5.8 by Weight
Dans un réacteur de polymérisation sont introduits 87,3 kg (332,8 mol) de sel N (sel 1 :1 d'hexaméthylène diamine et d'acide adipique), 3219 g d'acide 5- hydroxyisophtalique à 99,5% (HIA) (17,5 mol), 6276 g d'une solution d'hexaméthylène diamine (HMD) en solution dans l'eau à 32,4 % en poids (17,5 mol) et 81 ,2 kg d'eau déminéralisée et 6,4 g d'agent antimousse Silcolapse 5020®. Le copolyamide est fabriqué selon un procédé standard de polymérisation de type polyamide 66, avec 35 minutes de finition.  In a polymerization reactor are introduced 87.3 kg (332.8 mol) of salt N (1: 1 salt of hexamethylenediamine and adipic acid), 3219 g of 99.5% 5-hydroxyisophthalic acid ( HIA) (17.5 mol), 6276 g of a solution of hexamethylenediamine (HMD) in solution in water at 32.4% by weight (17.5 mol) and 81.2 kg of demineralized water and 6.4 g of Silcolapse 5020® Antifoam. The copolyamide is manufactured according to a standard polyamide 66 polymerization process, with 35 minutes of finishing.
Le polymère obtenu est coulé sous forme de jonc, refroidi et mis sous forme de granulé par coupe des joncs. The polymer obtained is cast in the form of rod, cooled and granulated by cutting rushes.
Le polymère obtenu présente les caractéristiques suivantes : GTC = 78,4 meq/kg, GTA = 57,6 meq/kg, Mn = 14 700 g/mol. The polymer obtained has the following characteristics: GTC = 78.4 meq / kg, GTA = 57.6 meq / kg, Mn = 14,700 g / mol.
Le copolyamide est semi-cristallin et a les caractéristiques thermiques suivantes : Tg= 76,8 °C, Tc= 218,4 °C, Tf= 256,2 °C, ΔΗί = 62,5 J/g. Le copolyamide a une Tg supérieure de 6,2 °C par rapport à celle du PA 66. Exemple 2 : préparation d'un copolyamide PA 66/6HIA 85/15 molaire ou 83/17 en poids The copolyamide is semi-crystalline and has the following thermal characteristics: Tg = 76.8 ° C, Tc = 218.4 ° C, Tm = 256.2 ° C, ΔΗί = 62.5 J / g. The copolyamide has a higher Tg of 6.2 ° C than that of PA 66. Example 2 Preparation of a PA 66 / 6HIA 85/15 Molar Copolyamide or 83/17 by Weight
Dans un réacteur de polymérisation sont introduits 76,9 kg (293,1 mol) de sel N (sel 1 :1 d'hexaméthylène diamine et d'acide adipique), 9462 g d'acide 5- hydroxyisophtalique à 99,5% (HIA) (51 ,7 mol), 18624 g d'une solution d'hexaméthylène diamine (HMD) en solution dans l'eau à 32,25 % en poids (51 ,7 mol) et 72,6 kg d'eau déminéralisée et 6,4 g d'agent antimousse Silcolapse 5020®. Le copolyamide est fabriqué selon un procédé standard de polymérisation de type polyamide 66, avec 35 minutes de finition.  76.9 kg (293.1 mol) of salt N (1: 1 salt of hexamethylenediamine and adipic acid), 9462 g of 99.5% 5-hydroxyisophthalic acid are introduced into a polymerization reactor ( HIA) (51.7 mol), 18624 g of a solution of hexamethylenediamine (HMD) in solution in water at 32.25% by weight (51.7 moles) and 72.6 kg of demineralized water and 6.4 g of Silcolapse 5020® Antifoam. The copolyamide is manufactured according to a standard polyamide 66 polymerization process, with 35 minutes of finishing.
Le polymère obtenu est coulé sous forme de jonc, refroidi et mis sous forme de granulé par coupe des joncs. The polymer obtained is cast in the form of rod, cooled and granulated by cutting rushes.
Le polymère obtenu présente les caractéristiques suivantes : GTC = 82,7 meq/kg, GTA = 61 ,5 meq/kg, Mn = 13 870 g/mol. The polymer obtained has the following characteristics: GTC = 82.7 meq / kg, GTA = 61.5 meq / kg, Mn = 13 870 g / mol.
Le copolyamide est semi-cristallin et a les caractéristiques thermiques suivantes : Tg= 85,8 °C, Tc= 186,2 °C, Tf= 240,4 °C, AHf = 41 ,9 J/g. Le copolyamide a une Tg supérieure de 15,2 °C par rapport à celle du PA 66. The copolyamide is semi-crystalline and has the following thermal characteristics: Tg = 85.8 ° C, Tc = 186.2 ° C, Tm = 240.4 ° C, AHf = 41.9 J / g. The copolyamide has a higher Tg of 15.2 ° C than that of PA 66.
Ce copolyamide présente une viscosité fondue η de 37 Pa.s. Exemple 3 : préparation d'un polyamide PA 6HIA et de mélange PA 66/PA 6HIA 85/15 en poids This copolyamide has a melt viscosity η of 37 Pa.s. Example 3 Preparation of a PA 6HIA Polyamide and of PA 66 / PA 6HIA 85/15 by Weight
Un sel 6HIA à 51 % en poids dans l'eau est réalisé par mélange d'un quantité stoechiométrique d'hexaméthylène diamine et d'acide 5-hydroxyisophtalique dans l'eau. Dans un réacteur de polymérisation sont ensuite introduits 5623 g de sel 6HIA à 51 %, 1 12,1 g d'acide 5-hydroxyisophtalique à 99,5%, 105 g d'eau et 3,3 g d'agent antimousse. Le polyamide PA 6HIA est fabriqué selon un procédé standard de polymérisation de type polyamide 66, avec 30 minutes de finition. Le polymère obtenu est coulé sous forme de jonc, refroidi et mis sous forme de granulé par coupe des joncs. Le polymère obtenu est amorphe et présente une température de transition vitreuse de Tg= 166,6 °C. A 51% by weight 6HIA salt in water is made by mixing a stoichiometric amount of hexamethylene diamine and 5-hydroxyisophthalic acid in water. 5623 g of 51% 6HIA salt, 12.1 g of 99.5% 5-hydroxyisophthalic acid, 105 g of water and 3.3 g of antifoaming agent are then introduced into a polymerization reactor. Polyamide PA 6HIA is manufactured according to a standard polyamide 66 polymerization process, with 30 minutes of finishing. The polymer obtained is cast in the form of rod, cooled and granulated by cutting rushes. The polymer obtained is amorphous and has a glass transition temperature of Tg = 166.6 ° C.
Le PA 66 et le PA 6HIA ainsi préparé sont mélangés dans une proportion 85/15 en poids en voie fondu dans un micro-extrudeur (« micro-compounder ») DSM MIDI 2000 (15 cm3) à une température de 275° C. Ce mélange présente une viscosité fondue η de 35 Pa.s. The PA 66 and the PA 6HIA thus prepared are mixed in a proportion of 85/15 by weight in the melt in a DSM MIDI 2000 micro-compounder ("micro-compounder") (15 cm 3 ) at a temperature of 275 ° C. This mixture has a melt viscosity η of 35 Pa.s.
Un autre mélange avec une proportion de 50/50 en poids est également préparé. Ce mélange présente une viscosité fondue η de 10 Pa.s. Exemple 4 : préparation d'un polyamide PA 66 fonctionnalisé phénol par un monoacide-phénol Another mixture with 50/50 by weight is also prepared. This mixture has a melt viscosity η of 10 Pa.s. EXAMPLE 4 Preparation of an PA 66 Polyamide Functionalized Phenol by a Monoacid-Phenol
Dans un réacteur de polymérisation sont introduits 135,2 g de sel N (0,52 mol), 9,41 g d'acide 4-hydroxyphénylacétique à 98 % (0,06 mol), 10,87 g d'une aqueuse solution d'hexaméthylène diamine à 32,4% (0,03 mol) et 127,2 g d'eau déminéralisée et 2 g d'un agent antimousse.  135.2 g of N salt (0.52 mol), 9.41 g of 4-hydroxyphenylacetic acid at 98% (0.06 mol) and 10.87 g of an aqueous solution are introduced into a polymerization reactor. 32.4% hexamethylene diamine (0.03 mol) and 127.2 g of demineralized water and 2 g of an antifoaming agent.
Le polyamide est fabriqué selon un procédé standard de polymérisation de type polyamide 66 avec 30 minutes de finition. Le polymère obtenu est coulé sous forme de jonc, refroidi et mis sous forme de granulé par coupe des joncs. The polyamide is manufactured according to a standard polyamide 66 polymerization process with 30 minutes of finishing. The polymer obtained is cast in the form of rod, cooled and granulated by cutting rushes.
Le polymère obtenu présente les caractéristiques suivantes : The polymer obtained has the following characteristics:
GTC = 103,3 meq/kg, GTA = 29,4 meq/kg. On calcule la quantité théorique de fonctions phénol en extrémité de chaîne GTP d'après les quantités initiales introduites dans le réacteur. GTP = 437 meq/kg. Mn = 2.106/(GTA + GTC + GTP) = 3510 g/mol . Le polyamide PA 66 fonctionnalisé phénol par l'acide 4-hydroxyphenylacétique est semi-cristallin et a les caractéristiques thermiques suivantes : Tc= 231 ,9 °C, Tf= 259 °C, DHf = 81 ,5 J/g. GTC = 103.3 meq / kg, GTA = 29.4 meq / kg. The theoretical amount of phenol functions at the GTP chain end is calculated from the initial amounts introduced into the reactor. GTP = 437 meq / kg. Mn = 2.10 6 / (GTA + GTC + GTP) = 3510 g / mol. The PA 66 polyamide functionalized phenol with 4-hydroxyphenylacetic acid is semi-crystalline and has the following thermal characteristics: Tc = 231.9 ° C, Tf = 259 ° C, DHf = 81.5 J / g.
Exemple 5 : Préparation des composites Example 5 Preparation of Composites
Les différents polymères considérés sont utilisés sous forme de poudre pour les plus fluides, sinon sous forme de film. Les poudres sont obtenues par broyage cryogénique, soit dans la carboglace, soit dans l'azote liquide. Les films sont réalisés par extrusion de granulés sur une extrudeuse Leistritz bivis de diamètre 34 et de L/D 34 équipée d'une filière plate et d'une filmeuse (débit d'extrudeuse de 10 Kg/h, vitesse de vis 250 rpm; température de 270°C). L'écartement des lèvres de la filière est de 300 μιτι environ pour une largeur de 30 cm avec une vitesse d'appel de 3,2 m/min sur rouleaux régulés à 1 15°C : les films obtenus ont une épaisseur qui varie entre 160 et 180 μιτι (bobines de largeur 300 mm).  The various polymers considered are used in powder form for the most fluid, if not in film form. The powders are obtained by cryogenic grinding, either in dry ice or in liquid nitrogen. The films are made by extrusion of granules on a Leistritz twin-screw extruder 34 and L / D 34 equipped with a flat die and a film-forming machine (extruder flow rate 10 Kg / h, screw speed 250 rpm; temperature of 270 ° C). The spacing of the lips of the die is about 300 μιτι for a width of 30 cm with a call speed of 3.2 m / min on rolls regulated at 1 15 ° C: the films obtained have a thickness that varies between 160 and 180 μιτι (coils of width 300 mm).
Les films polymères sont découpés sous forme de feuilles de 150x150 mm ou 200x300 mm, à partir des bobines précédemment obtenues. Il en est de même pour les tissus de renfort. The polymer films are cut into sheets of 150x150 mm or 200x300 mm, from the previously obtained coils. It is the same for reinforcement fabrics.
La réalisation des pièces composites est faite au moyen d'une presse hydraulique à double plateaux contrôlés en température Schwabenthan (Polystat 300A) : plateaux chauffants (résistances chauffantes), et plateaux refroidis (circulation d'eau). Un moule métallique dotée d'une empreinte de dimensions 150 mm x 150 mm ou 200x300 mm est utilisé. Composite parts are produced using a Schwabenthan (Polystat 300A) temperature-controlled dual-plate hydraulic press: hot plates (heating resistors) and cooled trays (water circulation). A metal mold with a print size of 150 mm x 150 mm or 200x300 mm is used.
Pour réaliser un composite contenant 80 % poids (65 % volume) de fibres de verre avec le tissus de grammage 600 g/m2, on introduit dans le moule une préforme constituée d'un empilement alterné comprenant 6 feuilles de tissus de verre et entre chaque soit une feuille de polymère, soit de la poudre uniformément répartie, les deux couches externes étant des feuilles de tissus de verre. La température des plateaux de la presse est préalablement montée à 290°C avant l'introduction de la préforme. A cette température, la pression est appliquée entre 1 et 50 bar et maintenue à cette valeur ; des dégazages sont rapidement effectués. L'ensemble est maintenu à la même température et pression, sans dégazage. A nouveau, il est effectué ensuite une série de dégazages, puis un maintien toujours à même température et pression. Le moule est alors transféré sur le dispositif plateaux refroidis et maintenu à une pression comprise entre 1 et 50 bar. Les pièces composites ainsi obtenues ont une dimension de 150x150 mm ou 200x300 mm et une épaisseur de 2 mm environ. In order to produce a composite containing 80% by weight (65% by volume) of glass fibers with the fabric weight of 600 g / m 2 , a preform consisting of an alternating stack comprising 6 sheets of glass fabric and between each is a polymer sheet, or evenly distributed powder, the two outer layers being sheets of glass fabrics. The temperature of the platens of the press is previously raised to 290 ° C before the introduction of the preform. At this temperature, the pressure is applied between 1 and 50 bar and maintained at this value; degassing is done quickly. The assembly is maintained at the same temperature and pressure, without degassing. Again, it is then carried out a series of degassing, then a maintenance always at the same temperature and pressure. The mold is then transferred to the cooled platen device and maintained at a pressure of between 1 and 50 bar. The composite parts thus obtained have a dimension of 150 × 150 mm or 200 × 300 mm and a thickness of about 2 mm.
Exemple 6 : Caractérisation des composites Example 6 Characterization of Composites
Un type de cycle a été réalisé : cycle de 5 min sous pression moyenne de 15 à 50 bar (1 min. sous 15 bar, puis 2 min sous 50 bar, puis 2 min sous 50 bar). Ce temps correspond à la durée totale du cycle entre la mise en température du moule et le refroidissement sous pression.  One type of cycle was carried out: cycle of 5 min under average pressure of 15 to 50 bar (1 min at 15 bar, then 2 min at 50 bar, then 2 min at 50 bar). This time corresponds to the total cycle time between the temperature setting of the mold and the cooling under pressure.
Les plaques 150x150 mm ou 200x300 mm sont découpées afin d'obtenir des échantillons de dimensions 150x20x2 mm. The sheets 150x150 mm or 200x300 mm are cut to obtain samples of dimensions 150x20x2 mm.
Une première série d'échantillon sont caractérisés juste après fabrication (échantillon mis sous enveloppe étanche, afin de les maintenir dans un état sec RHO). A first series of samples are characterized just after manufacture (sample placed in a sealed envelope, in order to keep them in a dry state RHO).
Un traitement de conditionnement peut également être réalisé selon la norme ISO1 1 10 "plastique/ polyamide/ conditionnement accéléré d'éprouvettes" : état dit RH50. La teneur en eau à l'équilibre est obtenue par conditionnement des pièces composites avec un cycle de 14 jours, à 70°C sous une humidité résiduelle RH de 62%. Les propriétés mécaniques ont été obtenues à 23°C, et humidité ambiante RH = 50%. A conditioning treatment can also be carried out according to the ISO1 1 10 standard "plastic / polyamide / accelerated conditioning of specimens": state said RH50. The equilibrium water content is obtained by conditioning the composite parts with a cycle of 14 days, at 70 ° C. under a residual humidity RH of 62%. The mechanical properties were obtained at 23 ° C, and humidity RH = 50%.
Les essais de flexion 3 points à température ambiante sont réalisés sur des éprouvettes parrallépipédiques (150x20x2 mm), selon la norme ISO N° 14125, sur une machine ZWICK 1478 : entre-axe de 64 mm, vitesse de traverse de 5 mm/min. Les valeurs de module élastique E de Young (GPa) et de contrainte σ max au pic (MPa) sont mesurées et calculées. Les essais de traction directe à température ambiante sont réalisés sur des éprouvettes parallépipédiques (250x25x2mm), selon la norme ASTM D3039/D3039M sur une machine ZWICK 1478 : vitesse de traverse de 1 à 5 mm/min. Les valeurs de module élastique de Young E (GPa) et de contrainte au pic amax (MPa) sont mesurées et calculées. The 3-point bending tests at room temperature are carried out on parallepipedic specimens (150x20x2 mm), according to ISO standard No. 14125, on a ZWICK 1478 machine: 64 mm center distance, 5 mm / min crosshead speed. Young's elastic modulus E (GPa) and maximum stress σ max (MPa) values are measured and calculated. Direct tensile tests at room temperature are carried out on parallelepipedal specimens (250x25x2mm), according to ASTM D3039 / D3039M on a ZWICK 1478 machine: crosshead speed of 1 to 5 mm / min. The elastic modulus values of Young E (GPa) and amax peak stress (MPa) are measured and calculated.
Les résultats sont mentionnés dans le tableau 1 suivant : The results are mentioned in the following table 1:
Tableau 1 Table 1
Résultats pour les pièces fabriquées selon Cycle pression moyenne (RHO / RH50)  Results for parts manufactured according to Medium pressure cycle (RHO / RH50)
Flexion 3 pts Traction  Bending 3 pts Traction
Module Contrainte Module Contrainte Constraint Module Constraint Module
Polyamide Polyamide
élastique E σ max élastique E omax utilisé  elastic E σ max elastic E omax used
(GPa) (MPa) (GPa) (MPa) (GPa) (MPa) (GPa) (MPa)
PA C1 RH50 27 610 27 498PA C1 RH50 27 610 27 498
RHO 29,1 650 29 520RHO 29.1 650 29 520
PA 3 (15%) PA 3 (15%)
29 600 28 550 RHO 29 600 28 550 RHO
PA 3 (50%) PA 3 (50%)
28,5 650 - - RHO 28.5 650 - - RHO
PA 2 RHO 28 590 - - Dans le cas d'un cycle de fabrication 5 minutes sous pression moyenne, les performances mécaniques obtenues sont élevées : contrainte max (pic) en flexion de 550 à 650 MPa, pour des valeurs de module entre 27 à 29 GPa. Pour les polyamides modifiés contenant des motifs hydroxyaromatiques 6HIA, on observe un léger gain de performance au niveau de la contrainte à rupture. Le mode de rupture en traction est nettement plus brutal que dans le cas des polyamides non modifiés. Exemple 7 : Caractérisation des composites après vieillissement hygrothermique PA 2 RHO 28 590 - - In the case of a 5 minute manufacturing cycle under average pressure, the mechanical performances obtained are high: max stress (peak) in bending of 550 to 650 MPa, for modulus values between 27 to 29 GPa. For the modified polyamides containing 6HIA hydroxyaromatic units, there is a slight improvement in performance at the breaking stress. The tensile failure mode is significantly more abrupt than in the case of unmodified polyamides. Example 7 Characterization of Composites After Hygrothermal Aging
Les échantillons préparés selon l'Exemple 6 ont été soumis à un vieillissement hygrothermique. Un vieillissement type accéléré a été réalisé par immersion des échantillons dans l'eau à 80°C, pendant 8 jours (test accéléré).  The samples prepared according to Example 6 were subjected to hygrothermal aging. Accelerated type aging was performed by immersing the samples in water at 80 ° C. for 8 days (accelerated test).
Après vieillissement, les éprouvettes ont été soit testées telle quelles, soit reconditionnées par élimination de l'eau adsorbée : traitement à 80°C sous vide pendant 24h (état sec : RHO). Les propriétés mécaniques ont été mesurées à 23°C, et humidité ambiante RH = 50% (éprouvettes telles quelles ou à RH = 0). After aging, the test pieces were either tested as is, or reconditioned by removal of the adsorbed water: treatment at 80 ° C under vacuum for 24 hours (dry state: RHO). The mechanical properties were measured at 23 ° C., and ambient humidity RH = 50% (specimens as such or RH = 0).
Les résultats sont mentionnés dans le tableau 2 suivant : The results are shown in Table 2 below:
Tableau 2 : Table 2:
Résultats pour les pièces fabriquées après vieillissement hygrothermique accéléré (80°C), état tel quel, et reconditionnement RHO  Results for parts manufactured after accelerated hygrothermal aging (80 ° C), as is, and reconditioning RHO
Dans le cas des polyamides haute fluidité ne contenant pas de motifs hydroxyaromatique 6HIA, on observe une chute des performances mécaniques notamment de la contrainte max (contrainte à rupture) : la contrainte maximale mesurée en flexion passe ainsi de 610 (RH50) à 340 MPa (tel quel), sinon de 650 (RHO) à 450 (RHO).soit une chute de 45% (état humide) ou 30% (RHO). In the case of high fluidity polyamides not containing 6HIA hydroxyaromatic units, there is a drop in the mechanical performance, in particular of the max stress (breaking stress): the maximum stress measured in flexion thus increases from 610 (RH50) to 340 MPa ( as is), otherwise from 650 (RHO) to 450 (RHO) is a drop of 45% (wet state) or 30% (RHO).
En présence de 15% PA HIA, on observe une nette amélioration des performances mécaniques après vieillissement hygrothermique. Le vieillissement induit alors une chute de la tenue mécanique en flexion limitée de 3% (blend PA 66/PA 6HIA 85/15) ou 15% (blend PA 66/PA 6HIA 50/50). In the presence of 15% PA HIA, there is a clear improvement in mechanical performance after hygrothermal aging. Aging then induces a drop in the limited flexural strength of 3% (blend PA 66 / PA 6HIA 85/15) or 15% (blend PA 66 / PA 6HIA 50/50).
Un comportement similaire est observé en traction directe : chute de la tenue mécanique en traction limitée à 7% pour le blend PA 66/PA 6HIA 85/15 (RHO). A similar behavior is observed in direct traction: fall in tensile strength limited to 7% for PA 66 / PA 6HIA 85/15 (RHO) blend.

Claims

REVENDICATIONS
1 . Procédé de fabrication d'un article composite comprenant au moins : 1. A method of manufacturing a composite article comprising at least:
a) une étape d'imprégnation d'une étoffe de renfort avec une composition polyamide à l'état fondu, ledit polyamide comprend des motifs hydroxyaromatiques chimiquement liés à la chaîne du polyamide, la composition comprenant une résine novolaque ; a) a step of impregnating a reinforcing fabric with a polyamide melt composition, said polyamide comprises hydroxyaromatic units chemically bonded to the polyamide chain, the composition comprising a novolak resin;
b) une étape de refroidissement et ensuite de récupération de l'article composite. b) a step of cooling and then recovering the composite article.
2. Procédé selon la revendication 1 , caractérisé en ce que la composition polyamide présente une viscosité fondue η comprise entre 1 et 50 Pa.s. 2. Method according to claim 1, characterized in that the polyamide composition has a melt viscosity η of between 1 and 50 Pa.s.
3. Procédé selon la revendication 1 ou 2, caractérisé en ce que la viscosité en fondue est mesurée à l'aide d'un rhéomètre plan-plan de diamètre 50 mm, sous un balayage en cisaillement par pallier allant de 1 à 160 s-1 , par fusion d'un film de polyamide d'une épaisseur 150 m à une température de 25 à 30°C au dessus de son point de fusion. 3. Method according to claim 1 or 2, characterized in that the melt viscosity is measured using a plane-plane rheometer diameter of 50 mm, under a sweep in step shear ranging from 1 to 160 s- 1, by melting a polyamide film with a thickness of 150 m at a temperature of 25 to 30 ° C above its melting point.
4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que le polyamide est choisi dans le groupe comprenant les polyamides obtenus par polycondensation d'au moins un diacide carboxylique aliphatique linéaire avec une diamine aliphatique ou cyclique ou entre au moins un diacide carboxylique aromatique et une diamine aliphatique ou aromatique, les polyamides obtenus par polycondensation d'au moins un aminoacide ou lactame sur lui-même, ou leur mélange et (co)polyamides. 4. Method according to any one of claims 1 to 3, characterized in that the polyamide is selected from the group comprising polyamides obtained by polycondensation of at least one linear aliphatic dicarboxylic acid with an aliphatic or cyclic diamine or between at least an aromatic dicarboxylic acid and an aliphatic or aromatic diamine, the polyamides obtained by polycondensation of at least one amino acid or lactam on itself, or their mixture and (co) polyamides.
5. Procédé selon la revendication 4, caractérisé en ce que le polyamide est obtenu par addition, avant ou pendant la polymérisation des monomères de polyamide, de monomères de types diamines, diacides carboxyliques, monoamines et/ou monoacides carboxyliques. 5. Process according to claim 4, characterized in that the polyamide is obtained by adding, before or during the polymerization of the polyamide monomers, monomers of diamine, dicarboxylic acid, monoamine and / or mono carboxylic acid types.
6. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que le polyamide est choisi dans le groupe comprenant le polyamide 6, le polyamide 66, le polyamide 6.10, le polyamide 1 1 , le polyamide 12, le polyamide 6.12, le poly(méta-xylylène adipamide), le polyamide 66/6T, le polyamide 66/61, les mélanges et copolyamides. 6. Method according to any one of claims 1 to 5, characterized in that the polyamide is chosen from the group comprising polyamide 6, polyamide 66, polyamide 6.10, polyamide 1 1, polyamide 12, polyamide 6.12. poly (meta-xylylene adipamide), polyamide 66 / 6T, polyamide 66/61, blends and copolyamides.
7. Procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce que le polyamide comprenant des motifs hydroxyaromatiques chimiquement liés à la chaîne du polyamide est obtenu par modification du polyamide avec un composé hydroxyaromatique. 7. Method according to any one of claims 1 to 6, characterized in that the polyamide comprising hydroxyaromatic units chemically bonded to the polyamide chain is obtained by modifying the polyamide with a hydroxyaromatic compound.
8. Procédé selon l'une quelconque des revendications 1 à 7, caractérisé en ce que le polyamide comprenant des motifs hydroxyaromatiques chimiquement liés à la chaîne du polyamide est obtenu par ajout en polymérisation d'un composé comprenant des motifs hydroxyaromatiques en présence des monomères du polyamide. 8. Process according to any one of Claims 1 to 7, characterized in that the polyamide comprising hydroxyaromatic units chemically bonded to the polyamide chain is obtained by adding to polymerization a compound comprising hydroxyaromatic units in the presence of the monomers of the polyamide.
9. Procédé selon les revendications 7 et 8, caractérisé en ce que le composé hydroxyaromatique présente au moins une fonction capable de réagir avec les fonctions du polyamide ou des monomères du polyamide. 9. Process according to claims 7 and 8, characterized in that the hydroxyaromatic compound has at least one function capable of reacting with the functions of the polyamide or monomers of the polyamide.
10. Procédé selon l'une quelconque des revendications 7 à 9, caractérisé en ce que le composé hydroxyaromatique est représenté par la formule suivante (I) : 10. Process according to any one of claims 7 to 9, characterized in that the hydroxyaromatic compound is represented by the following formula (I):
(HO)x-Z-(F)n (I) (HO) x -Z- (F) n (I)
dans laquelle : in which :
Z est un radical hydrocarboné aromatique ou arylaliphatique multivalent ; x est compris entre 1 et 10 ;  Z is a multivalent aromatic or arylaliphatic hydrocarbon radical; x is from 1 to 10;
F est une fonction acide, aldéhyde, aminé, cétone capable de se lier à une fonction acide ou aminé des monomères du polyamide ; et  F is an acid, aldehyde, amine, ketone function capable of binding to an acid or amine function of the monomers of the polyamide; and
- n est compris entre 1 et 5. n is between 1 and 5.
1 1 . Procédé selon la revendication 10, caractérisé en ce que Z est un radical multivalent est choisi dans le groupe comprenant : le benzène, le méthyle benzène, le naphtalène, le biphényle, le diphényle éther, le diphényle sulfure, le diphényle sulfone, le ditolyle éther, le xylylène, le diéthyl benzène, ou la pyridine. 1 1. Process according to claim 10, characterized in that Z is a multivalent radical is selected from the group consisting of: benzene, methyl benzene, naphthalene, biphenyl, diphenyl ether, diphenyl sulfide, diphenyl sulfone, ditolyl ether, xylylene, diethyl benzene, or pyridine.
12. Procédé selon l'une quelconque des revendications 7 à 1 1 , caractérisé en ce que le composé hydroxyaromatique est choisi dans le groupe comprenant : l'acide 2-hydroxytéréphtalique, l'acide 5-hydroxyisophtalique, l'acide 4- hydroxyisophtalique, l'acide 2,5-dihydroxytéréphtalique, l'acide 4- hydroxyphénylacétique ou l'acide gallique, la L-Tyrosine, l'acide 4- hydroxyphénylacétique, le 3,5-diaminophénol, le 5-hydroxy m-xylylène diamine, l'amino-3 phénol, l'amino-3 méthyl-4 phénol, et l'acide hydroxy-3 amino-5 benzoïque. 12. Process according to any one of claims 7 to 11, characterized in that the hydroxyaromatic compound is chosen from the group comprising: 2-hydroxyterephthalic acid, 5-hydroxyisophthalic acid, 4-hydroxyisophthalic acid, 2,5-dihydroxyterephthalic acid, 4-hydroxyphenylacetic acid or gallic acid, L-Tyrosine, 4-hydroxyphenylacetic acid, 3,5-diaminophenol, 5-hydroxy-m-xylylenediamine, 3-amino-phenol, 3-amino-4-methylphenol, and 3-hydroxy-5-amino-benzoic acid.
13. Procédé selon l'une quelconque des revendications 1 à 12, caractérisé en ce que les étoffes de renfort sont des réseaux fibreux ou filamenteux dont les fils et fibres sont choisis parmi les fils et/ou les fibres de carbone, de verre, d'aramides, de polyimides, de lin, de chanvre, de sisal, de coir, de jute, de kenaf et/ou de leur mélange. 13. Method according to any one of claims 1 to 12, characterized in that the reinforcing fabrics are fibrous or filamentary networks whose yarns and fibers are selected from son and / or carbon fibers, glass, d aramids, polyimides, flax, hemp, sisal, coir, jute, kenaf and / or their mixture.
14. Procédé selon l'une quelconque des revendications 1 à 13, caractérisé en ce que l'on injecte la composition polyamide dans une chambre de moulage comprenant au moins une étoffe de renfort pour réaliser l'imprégnation. 14. Method according to any one of claims 1 to 13, characterized in that the polyamide composition is injected into a molding chamber comprising at least one reinforcing fabric to perform the impregnation.
15. Procédé selon l'une quelconque des revendications 1 à 13, caractérisé en ce que l'on met en contact une ou plusieurs étoffes de renfort et un ou plusieurs films de polyamide et l'on réalise ladite imprégnation par fusion du polyamide. 15. A method according to any one of claims 1 to 13, characterized in that one or more reinforcing fabrics and one or more polyamide films are brought into contact and said melt impregnation of the polyamide is carried out.
16. Procédé selon l'une quelconque des revendications 1 à 13, caractérisé en ce que l'on met en contact une ou plusieurs étoffes de renfort et de la poudre d'un polyamide et l'on réalise ladite imprégnation par fusion du polyamide. 16. A method according to any one of claims 1 to 13, characterized in that one or more reinforcing fabrics and the powder of a polyamide is brought into contact and said melt impregnation of the polyamide is carried out.
17. Procédé selon l'une quelconque des revendications 1 à 13, caractérisé en ce que ledit procédé est un procédé de pultrusion. 17. Method according to any one of claims 1 to 13, characterized in that said method is a pultrusion process.
18. Procédé selon l'une quelconque des revendications 1 à 17, caractérisé en ce que l'article composite comprend de 25 à 80 % en volume d'étoffe de renfort par rapport au poids total de l'article. 18. Method according to any one of claims 1 to 17, characterized in that the composite article comprises 25 to 80% by volume of reinforcing fabric relative to the total weight of the article.
19. Article composite ou préforme obtenu par le procédé selon l'une quelconque des revendications 1 à 18. 19. Composite article or preform obtained by the process according to any one of claims 1 to 18.
EP11723366A 2010-05-17 2011-05-17 Composite polyamide article Withdrawn EP2571925A1 (en)

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FR1053779A FR2959995A1 (en) 2010-05-17 2010-05-17 COMPOSITE POLYAMIDE ARTICLE
PCT/EP2011/057934 WO2011144592A1 (en) 2010-05-17 2011-05-17 Composite polyamide article

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FR2959995A1 (en) 2011-11-18

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