WO2002066557A1 - Thermoplastic polymer composition based on polyamide - Google Patents

Thermoplastic polymer composition based on polyamide Download PDF

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Publication number
WO2002066557A1
WO2002066557A1 PCT/EP2002/001632 EP0201632W WO02066557A1 WO 2002066557 A1 WO2002066557 A1 WO 2002066557A1 EP 0201632 W EP0201632 W EP 0201632W WO 02066557 A1 WO02066557 A1 WO 02066557A1
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WO
WIPO (PCT)
Prior art keywords
compound
polyamide
composition according
styrene
compatibilization
Prior art date
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PCT/EP2002/001632
Other languages
French (fr)
Inventor
Yeong Chool Yu
Nicolangelo Peduto
Jung Hoon Park
Original Assignee
Rhodia Engineering Plastics S.R.L.
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Filing date
Publication date
Application filed by Rhodia Engineering Plastics S.R.L. filed Critical Rhodia Engineering Plastics S.R.L.
Priority to KR1020037010761A priority Critical patent/KR100573558B1/en
Priority to DE10295949T priority patent/DE10295949T5/en
Priority to JP2002566269A priority patent/JP2004521980A/en
Publication of WO2002066557A1 publication Critical patent/WO2002066557A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers

Definitions

  • the present invention relates to a thermoplastic polymer composition based on polyamide, having an excellent compromise in properties, in particular mechanical properties.
  • the composition exhibits in particular a high rigidity, a ductility or a high impact resistance, and a satisfactory behavior when it is subjected to relatively high temperatures.
  • thermoplastic material intended to be shaped by techniques such as injection, gas injection, extrusion, extrusion blow molding
  • rigidity e.g., the rigidity
  • dimensional stability in particular at relatively high temperature, low shrinkage after shaping, ability to be painted by different methods, surface appearance, density.
  • Polyamide is a polymer which is chemically resistant, which is stable at high temperatures and which can be mixed with other types of polymers in order to modify its properties. One can for example improve its resilience by adding an elastomeric polymer.
  • ABS Acrylonitrile-Butadiene-Styrene
  • these two incompatible polymers are generally compatibilized by maleic anhydride functions, carried by ABS or by another polymer.
  • the polyamide and ABS compositions thus compatibilized have properties linked to each of the compounds.
  • the document EP 648811 describes for example a mixture of polymers comprising polyamide (polyamide 6 or 66), ABS, a compatibilizer consisting of a Styrene-Maleimide polymer grafted with maleic anhydride, a grafted ethylene-propylene elastomer with maleic anhydride in an amount greater than 12%.
  • This mixture has excellent impact resistance at low temperature, and a high resistance to chemicals, due to polyamide.
  • the impact resistance at low temperature is mainly due to the very high content of grafted elastomeric compound.
  • the document does not describe the relative proportion of amino terminal groups and acid terminal groups. Compatibility between polyamide 66 and ABS is good but we are still trying to improve it.
  • the compromise in mechanical properties of the compositions described, in particular with regard to its low rigidity at room temperature may compromise its use for certain applications.
  • the presence of large amounts of grafted elastomeric compound makes the composition more expensive.
  • thermoplastic composition comprising the following compounds:
  • Compound A thermoplastic polyamide of the type of those obtained from diacids and diamines, the quantity of amino terminal groups being greater than the quantity of acid terminal groups.
  • Compound B copolymer comprising a rubber onto which are acrylonitrile and a styrene compound chosen from styrene and ⁇ -methyl-styrene, the copolymer comprising, where appropriate, functional groups for compatibilization with the polyamide,
  • Compound C where appropriate, one or more compatibilizing agent between the polyamide and the compound B, at least one of which comprises functional groups for compatibilization with the polyamide
  • Compound D where appropriate an elastomeric compound, the composition comprising at least one compound comprising groups functional compatibilization with polyamide.
  • composition according to the invention exhibits good compatibilization between compound A and compound B, with a compromise in interesting properties, at least at room temperature, in particular in terms of impact resistance, rigidity, temperature, deformation under filler, shrinkage on molding, surface appearance and paintability.
  • the compositions comprising little or no compound D, less than 10%, exhibit improved compatibilization, a compromise of improved properties at room temperature, especially high rigidity with sufficient impact resistance.
  • the surface appearance of these compositions is also excellent.
  • composition according to the invention can be obtained by mixing in the molten phase the various compounds.
  • An extrusion device can be used for this purpose, for example a single screw or double screw device.
  • compositions may contain other compounds. They may in particular be stabilization, reinforcement, pigmentation, fireproofing, catalysis compounds. They can also include mineral fillers, such as kaolin, wollastonite, talc, or reinforcing fibers such as glass or carbon fibers. These other compounds or fillers or fibers can be introduced into the composition during the stages of manufacture thereof or during the preparation of each of the compounds A and / or B and / or C and / or D.
  • the compositions according to The invention does not include mineral fillers or reinforcing fibers and presents a particularly interesting compromise between density and mechanical properties: the material exhibits high impact resistance and rigidity for a density which remains low.
  • the composition according to the invention preferably has a continuous polyamide phase in which are dispersed nodules comprising the compound B.
  • the composition advantageously comprises more polyamide than of compound B.
  • the polyamide and the compound B are not miscible .
  • the dispersion of compound B in the polyamide is facilitated by the presence of functional groups for compatibilization with the polyamide. These functional groups can be carried by compound B, or by a compatibilizing agent, generally miscible with compound B.
  • at least one of the compounds comprises such functional groups. Compatibility makes it possible to improve the behavior of the compositions.
  • composition may comprise other compounds than the compounds mentioned above.
  • polyamide of the type of those obtained from lactams and / or amino acids, for example polyamide 6.
  • It can also comprise a compound E, consisting of platelet mineral particles having a form factor greater than 5 and whose small dimension is less than 10 nm.
  • form factor is meant the ratio between the largest dimension characteristic of the shape of the particles and the smallest dimension characteristic of the shape of the particles.
  • the small dimension is the thickness.
  • the dispersed particles constituting a compound E are generally obtained from a compound having a structure in sheets. During the preparation of the composition, the sheets separate from each other so as to form the particles. The small particle size is substantially that of a sheet. The geometry of the particles, namely their shapes and dimensions can be observed in the compositions by microscopy, or be compared to that of the sheets of the compound from which they are obtained. As mentioned above, it is possible that the separation of the sheets is not complete and that agglomerates are present in the composition.
  • Compound A is a thermoplastic polyamide of the type of those obtained from diacids and diamines, the quantity of amino terminal groups being greater than the quantity of acid terminal groups.
  • polyamide 66 obtained from adipic acid and hexamethylene diamine. It is also possible to use a copolyamide comprising at least 75% of repeating units of the polyamide 66 type.
  • the compositions based on polyamide 66 have excellent mechanical properties and excellent properties of heat resistance, and high hardness. They are particularly suitable for painting processes by cataphoresis, which impose significant temperatures on the material.
  • polyamide 6 in the composition can make it possible in particular to reduce the shrinkage after shaping, to improve the compatibilization between the polyamide and the compound B and therefore to improve certain mechanical properties and / or surface properties.
  • the compound A used preferably polyamide 66, comprises more amino end groups than acid end groups.
  • the amount of amino terminal groups is preferably greater than 50 meq / kg and the difference between the amounts of amino terminal groups and of acid terminal groups is preferably greater than 5 meq / kg, even more preferably greater than 10 meq / kg.
  • the amounts of amino and / or acid end groups are determined by potentiometric assays after dissolution of the polyamide. A method is for example described in "Encyclopedia of Industrial Chemical Analysis", volume 17, page 293, 1973.
  • Compound B is a copolymer comprising a rubber on which are grafted acrylonitrile and a styrenic compound chosen from styrene and ⁇ -methyl-styrene.
  • This copolymer is thermoplastic. It may also contain functional groups intended to improve its compatibility with the polyamide.
  • the copolymer preferably comprises between 10 and 90% by weight of rubber.
  • the rubber content of all of compound B is preferably 15 to 35% by weight.
  • the rubber is preferably chosen from the group consisting of polybutadiene, butadiene-styrene rubber, butadiene-acrylate rubber, butadiene-acrylonitrile rubber, EPR (ethylene-propylene rubber) and EPDM (rubber of 'ethylene-propylene-diene) or mixtures of two or more of these rubbers.
  • Compound B can be prepared in the usual manner, for example by grafting the monomers of the styrenic compound and acryionitrile onto the rubber. This can be done by bulk, solution or suspension polymerization.
  • polymerization is preferably carried out in the presence of usual substances, such as free radical donors, optionally in combination with a redox system, chain regulating agents, stabilizing agents, suspending agents, emulsifiers and the like.
  • compound B is advantageously an Acrylonitrile-Butadiene- copolymer
  • the content by weight of butadiene in this compound is for example between 15 and 35%, the content by weight of styrene relative to the weight of styrene and acrylonitrile is preferably between 20 and 80%, preferably greater than 50 %. It may for example be an Acrylonitrile-Butadiene-Styrene copolymer, the proportions of Acrylonitrile, Butadiene and Styrene are approximately 25%, 25% and 50% respectively.
  • the compound B comprises functional groups for compatibilization with the polyamide. These groups are advantageously chosen from maleic anhydride, carboxylic acid and ester groups. Such groups are for example obtained by using a comonomer during the preparation of compound B, for example maleic anhydride or acrylamide.
  • compositions may comprise one or more compatibilization agent between the polyamide and the compound B. At least one of these agents comprises functional groups for compatibilization with the polyamide.
  • the mixture can either be obtained by an operation preceding the preparation of the composition, or can be obtained during the preparation of the composition by simultaneous or successive use of the various agents compatibilization.
  • the functional compatibilization groups present in at least one of the agents may be of the same nature as those optionally present in compound B. They are advantageously chosen from maleic anhydride, carboxylic acid and ester groups. Such groups are derived from a comonomer used during the preparation of compound C, for example maleic anhydride.
  • the compositions may not contain compound C.
  • the compositions may not contain functional groups for compatibilization with the polyamide.
  • styrene-Maleimides copolymers grafted with functional groups chosen from carboxylic acids and anhydrides.
  • styrene-maleimide copolymer is meant a polymer having units derived from styrene and maleimide units of formula (I)
  • R is chosen from hydrogen, alkyl radicals, aromatic or arylaromatic radicals.
  • R is for example a phenyl group.
  • the maleimide unit can for example be chosen from N-phenymaleimide, N- (o-methylphenyl maleimide), N- (m-methylphenyl maleimide), N- (p-methylphenyl maleimide).
  • Such copolymers can for example be obtained by copolymerization of styrene and maleic anhydride then partial reaction with an amine, for example aniline to form the maleimide units from the anhydride units.
  • the anhydride units which have not reacted with the amine constitute the functionalization.
  • Another method is to directly copolymerize styrene, maleimide and maleic anhydride.
  • compatibilizing agent are styrene-maleimide copolymers grafted with maleic anhydride, the proportions by weight of the different units of which are between 40 and 60% of styrene units, between 40 and 60% of N-phenylmaleimide units. , between 0.1 and 5% of maleic anhydride units.
  • These copolymers have particularly high mechanical and thermal properties, which makes the compositions particularly effective, in particular as regards the properties evaluated at relatively high temperatures.
  • composition can also comprise an ungrafted Styrene-Maleimide copolymer.
  • compatibilization agent By way of compatibilization agent, mention is also made of block copolymers of Styrene-Ethylene-Butadiene-Styrene or Styrene-Butadiene-Styrene, where appropriate totally or partially hydrogenated, having functional groups for compatibilization with the polyamide, for example anhydride functional groups. maleic. Such compounds are known to those skilled in the art. This type of copolymer is for example marketed by the company Shell under the Kraton range. Mention is more particularly made of the styrene-ethylene-butylene-styrene copolymer modified with maleic anhydride (SEBS - G - AM). The proportion by weight of this agent in the composition is advantageously between 0.5 and 10%. It is preferably less than 5%.
  • compatibilizing agent a styrene-acrylonitrile copolymer grafted with maleic anhydride, or even maleic anhydride introduced directly during the preparation of the composition.
  • compositions may include an elastomeric compound. Such compounds are generally used in order to modify the resilience of the compositions.
  • the proportion by weight of compound D in the composition is preferably less than or equal to 10% by weight.
  • this compound is grafted with functional groups chosen from carboxylic acids and acid anhydrides. The grafting of the copolymers with acid anhydride is generally obtained by copolymerization in the presence of maleic anhydride.
  • Elastomers which can be used as impact modifiers are defined as having an ASTM D-638 tensile modulus less than about 40,000, generally less than 25,000, and preferably less than 20,000. random, block or graft copolymers of homopolymers.
  • Useful rubbery polymers can be prepared from reactive monomers which can be part of the chains or branches of the polymer, or can be grafted onto the polymer. These reactive monomers can be dienes, carboxylic acids, and their derivatives, such as esters and anhydrides.
  • butadiene polymers examples include butadiene polymers, butadiene / styrene copolymers, isoprene, chloroprene, acrylonitrile / butadiene copolymers, isobutylene, isobutylene-butadiene copolymers, copolymers of ethylene / propylene (EPR), ethylene / propylene / diene copolymers (EPDM).
  • EPR ethylene / propylene
  • EPDM ethylene / propylene / diene copolymers
  • useful rubbery polymers mention may be made of polymers obtained from aromatic vinyl monomers, olefins, acrylic acid, methacrylic acid and their derivatives, and their metal salts. Useful rubbery polymers are described in US-A-4315086 and US-A-4174358.
  • a first preferred resilience modifier for carrying out the invention is a functionalized copolymer which is a copolymer of ethylene and an alpha-olefin other than ethylene, having a functionality such as a carboxyl or an anhydride, grafted on the ethylene copolymer.
  • the ethylene and the ⁇ -olefin are preferably a copolymer of ethylene and an ⁇ -olefin selected from an ⁇ -olefin at least C 3 -C 8 , and preferably C 3 -C 6 .
  • Propylene is preferred as the C 3 -C 8 ⁇ -olefin monomer in the copolymer.
  • C 3 -C 6 ⁇ -olefins such as 1-butene, 1-pentene, and 1-hexane, can be used instead of or in addition to propylene in the copolymers.
  • C 3 -C 6 ⁇ -olefins such as 1-butene, 1-pentene, and 1-hexane
  • ethylene-propylene rubbers grafted (functionalized) with maleic anhydride and ethylene-propylene-diene rubbers grafted (functionalized) with maleic anhydride .
  • the composition can comprise a compound E consisting of small, dispersed particles. These are generally obtained from a compound having a structure in sheets. During the preparation of the composition, the sheets separate from each other so as to form the particles. The separation of the sheets is often called exfoliation, dissociation and delamination. The processes involved in this separation can be different depending on the compounds used and / or the processes used. They lead to obtaining particles with a higher or lower form factor whose small dimension is less than 10 nm. The small dimension, for example the thickness of the particles is even more preferably less than 2 nm.
  • the compound with a platelet structure can be chosen from several families. Mention is made of fluoromicas, zirconium phosphates, silicates, more particularly phyllosilicates, hydrotalcites. Mention is made, as platelet silicates suitable for the implementation of the invention, of montmorillonites, smectites, illites, sepiolite, palygorkites, muscovites, ailervardites, amesites, hectorites, talcs, fluorohectorites, saponites, beidellites, nontronites, stevensites, bentonites, micas , fluoromicas, vermicullites, fluorovermicullites, halloysites. These compounds can be of natural, synthetic, or modified natural origin. Particularly preferred are montmorillonites.
  • the separation of the sheets into platelets can be favored by a preliminary treatment using an organic compound, for example an organic compound making it possible to increase the distance between the sheets.
  • the nature of the treatment may depend on the nature of the compound with sheet structure. Examples of treatments by ioniums, that is to say substituted ammoniums or phosphoniums, for the treatment of montmorillonites are cited as examples. Montmorillonites already treated are commercially available. Numerous treatments and / or methods for incorporating compounds with a sheet structure in thermoplastics, for example in polyamide, have been described. For the treatment of montmorillonites, and possibly other compounds with a sheet structure, mention is made in particular of the treatments by cation exchange initially contained in the compound.
  • organic cations of the ionium type can be chosen from phosphoniums and ammoniums, for example primary to quaternary ammoniums. Mention may be made, for example, of protonated amino acids such as protonated ammonium 12-aminododecanoic acid, protonated primary to tertiary amines and quaternary ammoniums.
  • the chains attached to the nitrogen or phosphorus atom of onium can be aliphatic, aromatic, arylaliphatic, linear or branched and can have oxygenated units, for example hydroxy or ethoxy units.
  • organic ammonium treatments examples include dodecy ammonium, octadecyl ammonium, bis (2-hydroxyethyl) octadecyl methyl ammonium, dimethyl dioctadecyl ammonium, octadecyl benzyl dimethyl ammonium, tetramethyl ammonium.
  • organic phosphonium treatments cite the alkyl phosphonium such as tetrabutyl phosphonium, trioctyl octadecyl phosphonium, octadecyl triphenyl phosphonium. These lists are in no way limiting.
  • the sheet silicates suitable for carrying out the invention can be chosen from montmorillonites, smectites, illites, sepiolite, palygorkites, muscovites, allervardites, amesites, hectorites, talcs, fluorohectorites, saponites, beidellites, nontronites, stevensites, bentonites, micas, fluoromicas, vermicullites, fluorovermicullites, halloysites. These compounds can be of natural, synthetic, or modified natural origin.
  • the compositions are composed of polyamide resin and platelet particles dispersed in the resin, obtained by exfoliation of a phyllosilicate, for example a montmorillonite having previously undergone a swelling treatment by exchange of ions.
  • a phyllosilicate for example a montmorillonite having previously undergone a swelling treatment by exchange of ions.
  • swelling treatments which can be used are for example described in patent EP 0398551. All the treatments known to promote the exfoliation of phyllosilicates in a polymer matrix can be used. It is possible, for example, to use a clay treated with an organic compound marketed by the company Laporte under the brand Cloisite®. It is also possible to use clays based on montmorillonites sold by the Nanocor Company under the Nanomer range.
  • a first method consists in mixing the compound with a sheet structure to be dispersed, optionally treated for example with a swelling agent, in the molten polymer and optionally subjecting the mixture to significant shearing, for example in a twin-screw extrusion device , in order to achieve good dispersion.
  • the polymer in question is understood either as one of the compounds taken individually, preferably polyamide, or as the mixture of the various compounds of the composition.
  • Another method consists in mixing the compound to be dispersed, optionally treated for example with a swelling agent, with the monomers in the polymerization medium, then in polymerizing. In this case, the polymer is preferably polyamide.
  • the platelet compound optionally treated is therefore introduced into a medium comprising polyamide monomers and then polymerized in order to obtain a polyamide (compound A) comprising compound E.
  • Another method consists in mixing with a molten polymer a concentrated mixture of a polymer and dispersed particles, prepared for example by one of the methods described above.
  • the proportions by weight of the various compounds are preferably as follows: Compound A: between 5 and 95%, preferably between 30 and 70%
  • Compound B between 5 and 95%, preferably between 20 and 40%
  • Compound C between 0 and 30%, preferably between 5 and 20%
  • Compound D between 0 and 30%, preferably less than 10%, for example between 1 and 10%
  • composition comprises a compound E
  • its proportion by weight is advantageously between 0.1 and 30%, preferably between 1 and 10%.
  • its proportion by weight relative to the total amount of polyamide in the composition is preferably less than 30%.
  • thermoplastic compositions are generally obtained by mixing the various compounds entering into the composition, the thermoplastic compounds being in molten form. We proceed at more or less high temperature, at more or less high shear force depending on the nature of the different compounds.
  • the compounds can be introduced simultaneously or successively.
  • An extrusion device is generally used in which the material is heated, subjected to a shearing force, and conveyed. Such devices are perfectly known to those skilled in the art.
  • all the compounds are mixed in the molten phase during a single operation, for example during an extrusion operation. It is possible, for example, to mix granules of polymeric materials, to introduce them into the extrusion device in order to melt them and subject them to more or less significant shearing.
  • a compound E or generally more exactly a compound with a piaquettary structure treated forming particles during the preparation of the composition, it is preferred in the context of this process to operate under relatively high shear in order to promote dissociation platelets.
  • the process for manufacturing the composition can comprise the following operations: a) preparation of a composite material comprising polyamide and the compound E b) mixing in the molten phase of the composite material, of the other compounds and, where appropriate, of polyamide not comprising compound E.
  • the composite material prepared in step a) can be obtained by one of the following methods: polymerization of polyamide in the presence of compound E in the form of particles or of a compound with a sheet structure optionally treated.
  • the polyamide thus prepared is preferably based on polyamide 6, the monomers being mainly chosen from caprolactam and / or 6-amino-caproic acid.
  • melt-blending of polyamide and of compound E in the form of particles or of a compound with a sheet structure possibly treated.
  • the mixing can be carried out using an extrusion device, preferably with high shear.
  • the composite material obtained in step a) constitutes a premix.
  • composition according to the invention when it is prepared using an extrusion device, is preferably packaged in the form of granules.
  • the granules is intended to be shaped using methods involving a fusion to obtain articles.
  • the articles are thus made up of the composition.
  • compositions according to the invention is particularly advantageous in the context of the manufacture of articles for the automotive industry, in particular for the manufacture of body parts.
  • - Compound A2 Polyamide 6, with a relative viscosity of 3.0, sold by the company Hyosung Corporation under the reference Toplamid 1021.
  • - Compound A3 Polyamide 66, with a viscosity index in 88% formic acid of 126, marketed by Rhodia Engineering Plastics under the reference Technyl 27A
  • Styrene-Maleimide (N-phenylmaleimide) copolymer grafted with maleic anhydride comprising 46% by weight of Styrene, 53% by weight of N-phenylmaleimide, 1% by weight of maleic anhydride, sold by the company Nippon Shokuba ⁇ under the reference PSX 0371.
  • Compound D1 Ethylene-Propylene elastomer grafted with maleic anhydride sold by the company Mitsui Chemical under the reference MP 0620.
  • compositions were prepared by mixing in the melt phase using a twin-screw extruder of the WERNER and PFLEIDERER ZSK type.
  • the extrusion conditions were as follows:
  • compositions obtained have excellent compatibilization between the polyamide and acrylonitrile-butadiene-styrene, mechanical properties and / or an improved surface appearance compared to compositions obtained from a polyamide 66, the amounts of terminal amino groups and acids are balanced, or which contain more acidic end groups than amino end groups.
  • compositions obtained have excellent compatibilization between the polyamide and acrylonitrile-butadiene-styrene, mechanical properties and / or an improved surface appearance compared to compositions obtained from a polyamide 66, the amounts of terminal amino groups and acids are balanced.

Abstract

The invention concerns a thermoplastic composition based on polyamide, exhibiting excellent balance of properties, in particular mechanical properties. The composition exhibits in particular high rigidity, high ductility or impact strength, and satisfactory behaviour when subjected to relatively high temperatures. The inventive composition comprises a polyamide of the type of those obtained from diacids and diamines and a copolymer including a rubber whereon are grafted acrylonitrile and a styrene compound.

Description

Composition polymère thermoplastique à base de polyamide Polyamide-based thermoplastic polymer composition
La présente invention concerne une composition polymère thermoplastique à base de polyamide, présentant un excellent compromis de propriétés, notamment de propriétés mécaniques. La composition présente en particulier une rigidité importante, une ductilité ou une résistance au choc importante, et un comportement satisfaisant lorsqu'elle est soumise à des températures relativement élevées.The present invention relates to a thermoplastic polymer composition based on polyamide, having an excellent compromise in properties, in particular mechanical properties. The composition exhibits in particular a high rigidity, a ductility or a high impact resistance, and a satisfactory behavior when it is subjected to relatively high temperatures.
Parmi les propriétés que l'on cherche souvent à contrôler pour un matériau thermoplastique destiné à être mis en forme par des techniques telles que l'injection, l'injection-gaz, l'extrusion, l'extrusion-soufflage, on cite la rigidité, la résistance aux chocs, la stabilité dimensionnelle, en particulier à température relativement élevée, le faible retrait après mise en forme, l'aptitude à la mise en peinture par différents procédés, l'aspect de surface, la densité. Ces propriétés peuvent être contrôlées, dans certaines limites, par le choix d'un polymère ou par l'adjonction au polymère de composés de différentes natures. Dans ce dernier cas, on parle de compositions polymères. Le choix d'un matériau pour une application donnée est généralement guidé par le niveau de performance exigé vis à vis de certaines propriétés et par son coût. On cherche toujours de nouveau matériaux susceptibles de répondre à un cahier des charges en terme de performance et/ou de coût. Le polyamide est par exemple un matériau largement utilisé, notamment dans le domaine de l'industrie automobile.Among the properties that one often seeks to control for a thermoplastic material intended to be shaped by techniques such as injection, gas injection, extrusion, extrusion blow molding, mention is made of the rigidity , impact resistance, dimensional stability, in particular at relatively high temperature, low shrinkage after shaping, ability to be painted by different methods, surface appearance, density. These properties can be controlled, within certain limits, by the choice of a polymer or by the addition to the polymer of compounds of different natures. In the latter case, we speak of polymer compositions. The choice of a material for a given application is generally guided by the level of performance required with regard to certain properties and by its cost. We are always looking for new materials capable of meeting specifications in terms of performance and / or cost. Polyamide is for example a widely used material, in particular in the field of the automobile industry.
Le polyamide est un polymère qui est résistant chimiquement, qui est stable à des températures élevées et qui peut être mélangé à d'autres types de polymères afin d'en modifier les propriétés. On peut par exemple améliorer sa résilience en ajoutant un polymère élastomérique.Polyamide is a polymer which is chemically resistant, which is stable at high temperatures and which can be mixed with other types of polymers in order to modify its properties. One can for example improve its resilience by adding an elastomeric polymer.
On connaît les mélanges de polymères comprenant du polyamide et de l'Acrylonitrile-Butadiène-Styrène (ABS). Dans ces mélanges, ces deux polymères, incompatibles, sont généralement compatibilisés par des fonctions anhydride maléique, portées par l'ABS ou par un autre polymère. Les compositions à base de polyamide et d'ABS ainsi compatibilisées présentent des propriétés liées à chacun des composés. Le document EP 648811 décrit par exemple un mélange de polymères comprenant du polyamide (polyamide 6 ou 66), de l'ABS, un compatibilisant constitué d'un polymère Styrène-Maléimide greffé avec de l'anhydride maléique, un élastomère éthylène- propylène greffé avec de l'anhydride maléique en quantité supérieure à 12%. Ce mélange présente une excellente résistance aux chocs à basse température, et une résistance élevée aux produits chimiques, due au polyamide. La résistance aux chocs à basse température est principalement due à la très forte teneur en composé élastomérique greffé. Le document ne décrit pas la proportion relative de groupements terminaux aminés et de groupements terminaux acides. La compatibilisation entre le polyamide 66 et l'ABS est bonne mais on cherche encore à l'améliorer. De plus, le compromis de propriétés mécaniques des compositions décrites, en particulier en ce qui concerne sa rigidité à la température ambiante, faible, peut compromettre son utilisation pour certaines applications. La présence de fortes quantités de composé élastomérique greffé rend de plus la composition coûteuse. On cherche un matériau à base de polyamide 66 présentant une meilleure compatibilisation et/ou un compromis de propriétés mécaniques modifié, présentant par exemple une rigidité plus importante à température ambiante avec une résistance aux chocs suffisante.Mixtures of polymers comprising polyamide and Acrylonitrile-Butadiene-Styrene (ABS) are known. In these blends, these two incompatible polymers are generally compatibilized by maleic anhydride functions, carried by ABS or by another polymer. The polyamide and ABS compositions thus compatibilized have properties linked to each of the compounds. The document EP 648811 describes for example a mixture of polymers comprising polyamide (polyamide 6 or 66), ABS, a compatibilizer consisting of a Styrene-Maleimide polymer grafted with maleic anhydride, a grafted ethylene-propylene elastomer with maleic anhydride in an amount greater than 12%. This mixture has excellent impact resistance at low temperature, and a high resistance to chemicals, due to polyamide. The impact resistance at low temperature is mainly due to the very high content of grafted elastomeric compound. The document does not describe the relative proportion of amino terminal groups and acid terminal groups. Compatibility between polyamide 66 and ABS is good but we are still trying to improve it. In addition, the compromise in mechanical properties of the compositions described, in particular with regard to its low rigidity at room temperature, may compromise its use for certain applications. The presence of large amounts of grafted elastomeric compound makes the composition more expensive. We are looking for a material based on polyamide 66 having better compatibilization and / or a modified compromise in mechanical properties, for example having greater rigidity at room temperature with sufficient impact resistance.
A cet effet, l'invention propose une composition thermoplastique comprenant les composés suivants:To this end, the invention provides a thermoplastic composition comprising the following compounds:
Composé A: polyamide thermoplastique du type de ceux obtenus à partir de diacides et de diamines, la quantité de groupements terminaux aminés étant supérieure à la quantité de groupements terminaux acides. Composé B: copolymère comprenant un caoutchouc sur lequel sont greffés de l'acrylonitrile et un composé styrènique choisi parmi le styrène et l'α-méthyle-styrène, le copolymère comprenant le cas échéant des groupements fonctionnels de compatibilisation avec le polyamide, Composé C: le cas échéant un ou plusieurs agent de compatibilisation entre le polyamide et le composé B, dont au moins un comprend des groupements fonctionnels de compatibilisation avec le polyamide Composé D: le cas échéant un composé élastomérique, la composition comprenant au moins un composé comprenant des groupements fonctionnels de compatibilisation avec le polyamide.Compound A: thermoplastic polyamide of the type of those obtained from diacids and diamines, the quantity of amino terminal groups being greater than the quantity of acid terminal groups. Compound B: copolymer comprising a rubber onto which are acrylonitrile and a styrene compound chosen from styrene and α-methyl-styrene, the copolymer comprising, where appropriate, functional groups for compatibilization with the polyamide, Compound C: where appropriate, one or more compatibilizing agent between the polyamide and the compound B, at least one of which comprises functional groups for compatibilization with the polyamide Compound D: where appropriate an elastomeric compound, the composition comprising at least one compound comprising groups functional compatibilization with polyamide.
La composition selon l'invention, présente une bonne compatibilisation entre le composé A et le composé B, avec un compromis de propriétés intéressant, au moins à température ambiante, notamment en terme de résistance aux chocs, de rigidité, de température, de déformation sous charge, de retrait au moulage, d'aspect de surface et de peignabiiité. Les compositions ne comprenant pas, ou comprenant peu, de composé D, moins de 10%, présentent une compatibilisation améliorée, un compromis de propriétés amélioré à température ambiante, notamment une rigidité importante avec une résistance aux chocs suffisante. L'aspect de surface de ces compositions est par ailleurs excellent.The composition according to the invention exhibits good compatibilization between compound A and compound B, with a compromise in interesting properties, at least at room temperature, in particular in terms of impact resistance, rigidity, temperature, deformation under filler, shrinkage on molding, surface appearance and paintability. The compositions comprising little or no compound D, less than 10%, exhibit improved compatibilization, a compromise of improved properties at room temperature, especially high rigidity with sufficient impact resistance. The surface appearance of these compositions is also excellent.
La composition selon l'invention peut être obtenue par mélange en phase fondue des différents composés. On peut utiliser à cet effet un dispositif d'extrusion, par exemple un dispositif simple vis ou double vis.The composition according to the invention can be obtained by mixing in the molten phase the various compounds. An extrusion device can be used for this purpose, for example a single screw or double screw device.
On précise que les compositions peuvent comporter d'autres composés. Il peut en particulier s'agir de composés de stabilisation, de renfort, de pigmentation, d'ignifugation, de catalyse. Elles peuvent également comporter des charges minérales, telles que du kaolin, de la wollastonite, du talc, ou des fibres de renfort telles que des fibres de verre ou de carbone. Ces autres composés ou charges ou fibres peuvent être introduits dans la composition lors des étapes de fabrication de celle-ci ou lors de la préparation de chacun des composés A et/ou B et/ou C et/ou D. Les compositions selon l'invention ne comprenant pas de charges minérales ou de fibres de renfort présentent un compromis entre la densité et les propriétés mécaniques particulièrement intéressant : le matériau présente une résistance aux chocs et une rigidité importantes pour une densité qui reste faible.It is specified that the compositions may contain other compounds. They may in particular be stabilization, reinforcement, pigmentation, fireproofing, catalysis compounds. They can also include mineral fillers, such as kaolin, wollastonite, talc, or reinforcing fibers such as glass or carbon fibers. These other compounds or fillers or fibers can be introduced into the composition during the stages of manufacture thereof or during the preparation of each of the compounds A and / or B and / or C and / or D. The compositions according to The invention does not include mineral fillers or reinforcing fibers and presents a particularly interesting compromise between density and mechanical properties: the material exhibits high impact resistance and rigidity for a density which remains low.
La composition selon l'invention présente de préférence une phase continue de polyamide dans laquelle sont dispersés des nodules comprenant le composé B. A cet effet la composition comporte avantageusement plus de polyamide que de composé B. Le polyamide et le composé B ne sont pas miscibles. La dispersion du composé B dans le polyamide est facilitée par la présence de groupements fonctionnels de compatibilisation avec le polyamide. Ces groupements fonctionnels peuvent être portés par le composé B, ou par un agent de compatibilisation, généralement miscible avec le composé B. Dans les compositions, au moins un des composés comprend de tels groupements fonctionnels. La compatibilisation permet d'améliorer le comportement des compositions.The composition according to the invention preferably has a continuous polyamide phase in which are dispersed nodules comprising the compound B. For this purpose the composition advantageously comprises more polyamide than of compound B. The polyamide and the compound B are not miscible . The dispersion of compound B in the polyamide is facilitated by the presence of functional groups for compatibilization with the polyamide. These functional groups can be carried by compound B, or by a compatibilizing agent, generally miscible with compound B. In the compositions, at least one of the compounds comprises such functional groups. Compatibility makes it possible to improve the behavior of the compositions.
La composition peut comprendre d'autre composés que les composés mentionnés ci-dessus.The composition may comprise other compounds than the compounds mentioned above.
Elle peut par exemple comprendre du polyamide du type de ceux obtenus à partir de lactames et/ou d'amino-acides, par exemple du polyamide 6.It can for example comprise polyamide of the type of those obtained from lactams and / or amino acids, for example polyamide 6.
Elle peut également comprendre un composé E, constitué des particules minérales plaquettaires présentant un facteur de forme supérieur à 5 et dont la petite dimension est inférieure à 10 nm. Par facteur de forme, on entend le rapport entre la plus grande dimension caractéristique de la forme des particules et la plus petite dimension caractéristique de la forme des particules. Pour des particules plaquettaires, la petite dimension est l'épaisseur. Ces particules sont dispersées dans la composition. La dispersion peut être de plus ou moins bonne qualité : il est possible que la composition présente des agglomérats de particules plaquettaires. Les particules sont préférentiellement dispersées dans le polyamide. Il est toutefois possible que des particules soient présentes dans les autres composés, par exemple dans le composé B.It can also comprise a compound E, consisting of platelet mineral particles having a form factor greater than 5 and whose small dimension is less than 10 nm. By form factor is meant the ratio between the largest dimension characteristic of the shape of the particles and the smallest dimension characteristic of the shape of the particles. For platelet particles, the small dimension is the thickness. These particles are dispersed in the composition. The dispersion can be of more or less good quality: it is possible that the composition has agglomerates of platelet particles. The particles are preferably dispersed in the polyamide. It is however possible that particles are present in the other compounds, for example in compound B.
Les particules, dispersées, constituant un composé E sont généralement obtenues à partir d'un composé présentant une structure en feuillets. Au cours de la préparation de la composition les feuillets se séparent les uns de autres pour ainsi former les particules. La petite dimension des particules est sensiblement celle d'un feuillet. La géométrie des particules, à savoir leurs formes et dimensions peut être observée dans les compositions par microscopie, ou être assimilée à celle des feuillets du composé à partir duquel elles sont obtenues. Comme mentionné plus haut, il est possible que la séparation des feuillets ne soit pas totale et que des agglomérats soient présents dans la composition.The dispersed particles constituting a compound E are generally obtained from a compound having a structure in sheets. During the preparation of the composition, the sheets separate from each other so as to form the particles. The small particle size is substantially that of a sheet. The geometry of the particles, namely their shapes and dimensions can be observed in the compositions by microscopy, or be compared to that of the sheets of the compound from which they are obtained. As mentioned above, it is possible that the separation of the sheets is not complete and that agglomerates are present in the composition.
On détaille à présent les différents composés de la composition.We now detail the different compounds of the composition.
Composé ACompound A
Le composé A est du polyamide thermoplastique du type de ceux obtenus à partir de diacides et de diamines, dont la quantité de groupements terminaux aminés est supérieure à la quantité de groupements terminaux acides.Compound A is a thermoplastic polyamide of the type of those obtained from diacids and diamines, the quantity of amino terminal groups being greater than the quantity of acid terminal groups.
On préfère tout particulièrement le polyamide 66, obtenu à partir d'acide adipique et d'hexaméthylène diamine. On peut également utiliser un copolyamide comprenant au moins 75% de motifs de répétition du type polyamide 66. Les compositions à base de polyamide 66 présentent d'excellentes propriétés mécaniques et d'excellentes propriétés de résistance à la chaleur, et une dureté importante. Elles sont particulièrement adaptées aux procédés de mise en peinture par cataphorèse, qui imposent au matériau des températures importantes.Particularly preferred is polyamide 66, obtained from adipic acid and hexamethylene diamine. It is also possible to use a copolyamide comprising at least 75% of repeating units of the polyamide 66 type. The compositions based on polyamide 66 have excellent mechanical properties and excellent properties of heat resistance, and high hardness. They are particularly suitable for painting processes by cataphoresis, which impose significant temperatures on the material.
La présence de polyamide 6 dans la composition peut permettre notamment de réduire le retrait après mise en forme, d'améliorer la compatibilisation entre le polyamide et le composé B et donc d'améliorer certaines propriétés mécaniques et/ou propriétés de surface.The presence of polyamide 6 in the composition can make it possible in particular to reduce the shrinkage after shaping, to improve the compatibilization between the polyamide and the compound B and therefore to improve certain mechanical properties and / or surface properties.
Selon une caractéristique de l'invention, le composé A utilisé, de préférence du polyamide 66, comprend plus de groupements terminaux aminés que de groupements terminaux acides. Une telle caractéristique améliore la compatibilisation, les propriétés mécaniques et/ou l'aspect de surface des articles constitués de la composition. La quantité de groupements terminaux aminés est de préférence supérieure à 50 meq/kg et la différence entre les quantités de groupements terminaux aminés et de groupements terminaux acides est de préférence supérieure à 5 meq/kg, encore plus préférablement supérieure à 10 meq/kg. Les quantités de groupements terminaux aminés et/ou acides sont déterminées par dosages potentiométriques après dissolution du polyamide. Une méthode est par exemple décrite dans "Encyclopedia of Industrial Chemical Analysis", volume 17, page 293, 1973.According to a characteristic of the invention, the compound A used, preferably polyamide 66, comprises more amino end groups than acid end groups. Such a characteristic improves the compatibilization, the mechanical properties and / or the surface appearance of the articles made up of the composition. The amount of amino terminal groups is preferably greater than 50 meq / kg and the difference between the amounts of amino terminal groups and of acid terminal groups is preferably greater than 5 meq / kg, even more preferably greater than 10 meq / kg. The amounts of amino and / or acid end groups are determined by potentiometric assays after dissolution of the polyamide. A method is for example described in "Encyclopedia of Industrial Chemical Analysis", volume 17, page 293, 1973.
Composé BCompound B
Le composé B est un copolymère comprenant un caoutchouc sur lequel sont greffés de l'acryionitrile et un composé styrenique choisi parmi le styrène et l'α-méthyle- styrène. Ce copolymère est thermoplastique. Il peut comporter en plus des groupements fonctionnels destinés à améliorer sa compatibilité avec le polyamide. Le copolymère comprend de préférence entre 10 et 90% en poids de caoutchouc. La teneur en caoutchouc de l'ensemble du composé B est de préférence de 15 à 35 % en poids. Le caoutchouc est de préférence choisi dans le groupe constitué par le polybutadiène, le caoutchouc butadiène-styrène, le caoutchouc butadiène-acrylate, le caoutchouc butadiène-acrylonitrile, l'EPR (caoutchouc d'éthylène-propylène) et l'EPDM (caoutchouc d'éthylène-propylène-diène) ou des mélanges de deux ou de plus de deux de ces caoutchoucs. Le composé B peut être préparé de la manière habituelle, par exemple par greffage des monomères du composé styrenique et de l'acryionitrile sur le caoutchouc. Ceci peut être effectué par polymérisation en masse, en solution ou en suspension. Il est également possible de combiner deux ou plus de deux de ces méthodes de polymérisation pour réaliser, par exemple, la polymérisation en masse en solution, la polymérisation en masse en suspension ou la polymérisation en émulsion-suspension. La polymérisation est de préférence réalisée en présence de substances habituelles, telles que des donneurs de radicaux libres, facultativement en combinaison avec un système redox, des agents régulateurs de chaîne, des agents stabilisants, des agents de mise en suspension, des émulsifiants et analogues. Le composé B est avantageusement un copolymère Acrylonitrile-Butadiène-Compound B is a copolymer comprising a rubber on which are grafted acrylonitrile and a styrenic compound chosen from styrene and α-methyl-styrene. This copolymer is thermoplastic. It may also contain functional groups intended to improve its compatibility with the polyamide. The copolymer preferably comprises between 10 and 90% by weight of rubber. The rubber content of all of compound B is preferably 15 to 35% by weight. The rubber is preferably chosen from the group consisting of polybutadiene, butadiene-styrene rubber, butadiene-acrylate rubber, butadiene-acrylonitrile rubber, EPR (ethylene-propylene rubber) and EPDM (rubber of 'ethylene-propylene-diene) or mixtures of two or more of these rubbers. Compound B can be prepared in the usual manner, for example by grafting the monomers of the styrenic compound and acryionitrile onto the rubber. This can be done by bulk, solution or suspension polymerization. It is also possible to combine two or more of two of these polymerization methods to carry out, for example, solution mass polymerization, suspension mass polymerization or emulsion-suspension polymerization. The polymerization is preferably carried out in the presence of usual substances, such as free radical donors, optionally in combination with a redox system, chain regulating agents, stabilizing agents, suspending agents, emulsifiers and the like. Compound B is advantageously an Acrylonitrile-Butadiene- copolymer
Styrène. Le teneur en poids de butadiène dans ce composé est par exemple comprise entre 15 et 35%, la teneur en poids de styrène par rapport au poids de styrène et d'acrylonitrile est de préférence comprise entre 20 et 80%, de préférence supérieure à 50%. Il peut par exemple s'agir d'un copolymère Acrylonitrile-Butadiène-Styrène dont les proportions en Acrylonitrile, Butadiène et Styrène sont respectivement d'environ 25%, 25% et 50%. Selon un mode de réalisation particulier, le composé B comprend des groupements fonctionnels de compatibilisation avec le polyamide. Ces groupements sont avantageusement choisis parmi les groupements anhydride maléique, acide carboxylique, ester. Des tels groupements sont par exemple obtenus par utilisation d'un comonomère lors de la préparation du composé B, par exemple de l'anhydride maléique ou de l'acrylamide.Styrene. The content by weight of butadiene in this compound is for example between 15 and 35%, the content by weight of styrene relative to the weight of styrene and acrylonitrile is preferably between 20 and 80%, preferably greater than 50 %. It may for example be an Acrylonitrile-Butadiene-Styrene copolymer, the proportions of Acrylonitrile, Butadiene and Styrene are approximately 25%, 25% and 50% respectively. According to a particular embodiment, the compound B comprises functional groups for compatibilization with the polyamide. These groups are advantageously chosen from maleic anhydride, carboxylic acid and ester groups. Such groups are for example obtained by using a comonomer during the preparation of compound B, for example maleic anhydride or acrylamide.
Composé CCompound C
Les compositions peuvent comporter un ou plusieurs agent de compatibilisation entre le polyamide et le composé B. Au moins un de ces agents comprend des groupements fonctionnels de compatibilisation avec le polyamide. Dans le cas où il s'agit de plusieurs agents, le mélange peut soit être obtenu par une opération précédant la préparation de la composition, soit être obtenu au cours de la préparation de la composition par mise en œuvre simultanée ou successive des différents agents de compatibilisation.The compositions may comprise one or more compatibilization agent between the polyamide and the compound B. At least one of these agents comprises functional groups for compatibilization with the polyamide. In the case of several agents, the mixture can either be obtained by an operation preceding the preparation of the composition, or can be obtained during the preparation of the composition by simultaneous or successive use of the various agents compatibilization.
Les groupements fonctionnels de compatibilisation présents dans au moins un des agents peuvent être de même nature que ceux éventuellement présents dans le composé B. Ils sont avantageusement choisis parmi les groupements anhydride maléique, acide carboxylique, ester. De tels groupements sont dérivés d'un comonomère utilisé lors de la préparation du composé C, par exemple de l'anhydride maléique.The functional compatibilization groups present in at least one of the agents may be of the same nature as those optionally present in compound B. They are advantageously chosen from maleic anhydride, carboxylic acid and ester groups. Such groups are derived from a comonomer used during the preparation of compound C, for example maleic anhydride.
Selon le mode de réalisation pour lequel le composé B comprend des groupements de compatibilisation avec le polyamide, les compositions peuvent ne pas comporter de composé C. Selon le mode de réalisation pour lequel les compositions comprennent un composé C, le composé B peut ne pas comporter de groupements fonctionnels de compatibilisation avec le polyamide.According to the embodiment for which the compound B comprises groups for compatibilization with the polyamide, the compositions may not contain compound C. According to the embodiment for which the compositions comprise a compound C, the compound B may not contain functional groups for compatibilization with the polyamide.
A titre d'agents de compatibilisation, on cite les copolymères Styrène-Maléïmides greffés avec des groupements fonctionnels choisis parmi les acides carboxyliques et les anhydrides. Par copolymère styrène-maléïmide, on entend un polymère présentant des motifs issus du styrène et des motifs maléimides de formule (I)By way of compatibilization agents, mention is made of the Styrene-Maleimides copolymers grafted with functional groups chosen from carboxylic acids and anhydrides. By styrene-maleimide copolymer is meant a polymer having units derived from styrene and maleimide units of formula (I)
Figure imgf000007_0001
dans laquelle R est choisi parmi l'hydrogène, les radicaux alkyles, les radicaux aromatiques ou arylaromatique. R est par exemple un groupement phényle. Le motif maléimide peut par exemple être choisi parmi le N-phénymaléimide, le N-(o- méthylphényle maléimide), le N-(m-méthylphényle maléimide), le N-(p-méthylphényle maléimide). De tels copolymères peuvent par exemple être obtenus par copolymérisation de styrène et d'anhydride maléique puis réaction partielle avec une aminé, par exemple l'aniline pour former les motifs maléimide à partir des motifs anhydride. Les motifs anhydrides n'ayant pas réagi avec l'aminé constituent la fonctionnalisation. Un autre procédé consiste à copolymériser directement du styrène, du maléimide et de l'anhydride maléique.
Figure imgf000007_0001
in which R is chosen from hydrogen, alkyl radicals, aromatic or arylaromatic radicals. R is for example a phenyl group. The maleimide unit can for example be chosen from N-phenymaleimide, N- (o-methylphenyl maleimide), N- (m-methylphenyl maleimide), N- (p-methylphenyl maleimide). Such copolymers can for example be obtained by copolymerization of styrene and maleic anhydride then partial reaction with an amine, for example aniline to form the maleimide units from the anhydride units. The anhydride units which have not reacted with the amine constitute the functionalization. Another method is to directly copolymerize styrene, maleimide and maleic anhydride.
On préfère tout particulièrement à titre d'agent de compatibilisation les copolymères Styrène-Maléimide greffés anhydride maléique, dont les proportions en poids des différents motifs sont comprises, entre 40 et 60 % de motifs styrène, entre 40 et 60 % de motifs N-phénylemaléimide, entre 0,1 et 5% de motifs anhydride maléique. Ces copolymères ont des propriétés mécaniques et thermiques particulièrement élevées, ce qui rend les compositions particulièrement performantes, en particulier en ce qui concerne les propriétés évaluées à des températures relativement élevées.Particularly preferred as compatibilizing agent are styrene-maleimide copolymers grafted with maleic anhydride, the proportions by weight of the different units of which are between 40 and 60% of styrene units, between 40 and 60% of N-phenylmaleimide units. , between 0.1 and 5% of maleic anhydride units. These copolymers have particularly high mechanical and thermal properties, which makes the compositions particularly effective, in particular as regards the properties evaluated at relatively high temperatures.
La composition peut comprendre également un copolymère Styrène-Maléïmide non greffé.The composition can also comprise an ungrafted Styrene-Maleimide copolymer.
A titre d'agent de compatibilisation on cite également les copolymères block Styrène-Ethylène-Butadiène-Styrène ou Styrène-Butadiène-Styrène le cas échéant totalement ou partiellement hydrogénés, présentant des groupements fonctionnels de compatibilisation avec le polyamide, par exemple des groupements fonctionnels anhydride maléique. De tels composés sont connus de l'homme du métier. Ce type de copolymères est par exemple commercialisé par la société Shell sous la gamme Kraton. On cite plus particulièrement le copolymère styrène-éthylène-butylène-styrène modifié avec de l'anhydride maléique (SEBS - G - AM). La proportion en poids de cet agent dans la composition est avantageusement comprise entre 0,5 et 10%. Elle est de préférence inférieure à 5%.By way of compatibilization agent, mention is also made of block copolymers of Styrene-Ethylene-Butadiene-Styrene or Styrene-Butadiene-Styrene, where appropriate totally or partially hydrogenated, having functional groups for compatibilization with the polyamide, for example anhydride functional groups. maleic. Such compounds are known to those skilled in the art. This type of copolymer is for example marketed by the company Shell under the Kraton range. Mention is more particularly made of the styrene-ethylene-butylene-styrene copolymer modified with maleic anhydride (SEBS - G - AM). The proportion by weight of this agent in the composition is advantageously between 0.5 and 10%. It is preferably less than 5%.
On peut avantageusement utiliser à titre d'agents de compatibilisation à la fois du Styrène-Maléimide greffé anhydride maléique et du SEBS greffé anhydride maléique.It is advantageous to use, as compatibilizers, both Styrene-Maleimide grafted maleic anhydride and SEBS grafted maleic anhydride.
On peut également utiliser à titre d'agent de compatibilisation un copolymère styrène-acrylonitriie greffé anhydride maléique, ou même de l'anhydride maléique introduit directement au cours de la préparation de la composition.It is also possible to use, as compatibilizing agent, a styrene-acrylonitrile copolymer grafted with maleic anhydride, or even maleic anhydride introduced directly during the preparation of the composition.
Composé DCompound D
Le compositions peuvent comporter un composé élastomérique. De tels composés sont généralement utilisés afin de modifier la résilience des compositions. La proportion en poids du composé D dans la composition est de préférence inférieure ou égale à 10% en poids. Selon une caractéristique préférentielle de l'invention ce composé est greffé avec des groupements fonctionnels choisis parmi les acides carboxyliques et les anhydrides d'acides. Le greffage par l'anhydride d'acide des copolymères est généralement obtenu par copolymérisation en présence d'anhydride maléique.The compositions may include an elastomeric compound. Such compounds are generally used in order to modify the resilience of the compositions. The proportion by weight of compound D in the composition is preferably less than or equal to 10% by weight. According to a preferred characteristic of the invention, this compound is grafted with functional groups chosen from carboxylic acids and acid anhydrides. The grafting of the copolymers with acid anhydride is generally obtained by copolymerization in the presence of maleic anhydride.
Les élastomères pouvant être utilisés en tant qu'agent modificateurs de la résilience sont définis comme ayant un module de traction ASTM D-638 inférieur à environ 40000, généralement inférieur à 25000, et de préférence, inférieur à 20000. Il peut s'agir de copolymères aléatoires, séquences ou greffés d'homopolymères. Des polymères caoutchouteux utiles peuvent être préparés à partir de monomères réactifs qui peuvent faire partie des chaînes ou ramifications du polymère, ou être greffés sur le polymère. Ces monomères réactifs peuvent être des diènes, des acides carboxyliques, et leurs dérivés, tels que des esters et des anhydrides. Parmi ces polymères caoutchouteux, on citera des polymères de butadiène, des copolymères de butadiène/styrène, l'isoprène, le chloroprène, des copolymères d'acrylonitrile/butadiène, l'isobutylène, des copolymères d'isobutylène-butadiène, des copolymères d'éthylène/propylène (EPR), des copolymères d'éthylène/propylène/diène (EPDM). Comme polymères caoutchouteux utiles, on peut citer les polymères obtenus à partir de monomères vinyliques aromatiques, d'oléfines, de l'acide acrylique, de l'acide méthacrylique et de leurs dérivés, et leurs sels métalliques. Des polymères caoutchouteux utiles sont décrits dans les brevets US-A-4315086 et US-A-4174358.Elastomers which can be used as impact modifiers are defined as having an ASTM D-638 tensile modulus less than about 40,000, generally less than 25,000, and preferably less than 20,000. random, block or graft copolymers of homopolymers. Useful rubbery polymers can be prepared from reactive monomers which can be part of the chains or branches of the polymer, or can be grafted onto the polymer. These reactive monomers can be dienes, carboxylic acids, and their derivatives, such as esters and anhydrides. Among these rubbery polymers, mention will be made of butadiene polymers, butadiene / styrene copolymers, isoprene, chloroprene, acrylonitrile / butadiene copolymers, isobutylene, isobutylene-butadiene copolymers, copolymers of ethylene / propylene (EPR), ethylene / propylene / diene copolymers (EPDM). As useful rubbery polymers, mention may be made of polymers obtained from aromatic vinyl monomers, olefins, acrylic acid, methacrylic acid and their derivatives, and their metal salts. Useful rubbery polymers are described in US-A-4315086 and US-A-4174358.
Un premier agent modificateur de la résilience préféré pour la réalisation de l'invention est un copolymère fonctionnalisé qui est un copolymère d'éthylène et d'une alpha-oléfine autre que l'éthylène, ayant une fonctionnalité comme un carboxyle ou un anhydride, greffée sur le copolymère d'éthylène. L'éthylène et l'α-oléfine sont de préférence un copolymère d'éthylène et d'une α-oléfine sélectionnée parmi une α-oléfine au moins en C3-C8, et de préférence, en C3-C6. On préfère le propylène comme monomère d'α-oléfine en C3-C8 dans le copolymère. D'autres α-oléfines en C3-C6, telles que le 1 -butène, le 1-pentène, et le 1-hexane, peuvent être utilisées au lieu ou en plus du propylène dans les copolymères. Pour la mise en œuvre de l'invention selon un mode préférentiel, on peut citer les caoutchoucs éthylène-propylène greffés (fonctionnalisés) par de l'anhydride maléique et les caoutchoucs éthylène-propylène-diènes greffés (fonctionnalisés) par le l'anhydride maléique.A first preferred resilience modifier for carrying out the invention is a functionalized copolymer which is a copolymer of ethylene and an alpha-olefin other than ethylene, having a functionality such as a carboxyl or an anhydride, grafted on the ethylene copolymer. The ethylene and the α-olefin are preferably a copolymer of ethylene and an α-olefin selected from an α-olefin at least C 3 -C 8 , and preferably C 3 -C 6 . Propylene is preferred as the C 3 -C 8 α-olefin monomer in the copolymer. Other C 3 -C 6 α-olefins, such as 1-butene, 1-pentene, and 1-hexane, can be used instead of or in addition to propylene in the copolymers. For the implementation of the invention according to a preferred embodiment, mention may be made of ethylene-propylene rubbers grafted (functionalized) with maleic anhydride and ethylene-propylene-diene rubbers grafted (functionalized) with maleic anhydride .
Composé ECompound E
Comme mentionné plus haut, la composition peut comporter un composé E constitué de particules de petite taille, dispersées. Celles-ci sont généralement obtenues à partir d'un composé présentant une structure en feuillets. Au cours de la préparation de la composition les feuillets se séparent les uns de autres pour ainsi former les particules. La séparation des feuillets est souvent dénommée exfoliation, dissociation et délamination. Les processus qui sont mis en jeu lors de cette séparation peuvent être différents selon les composés utilisés et/ou les procédés utilisés. Ils mènent à l'obtention de particules à facteur de forme plus ou moins élevé dont la petite dimension est inférieure à 10 nm. La petite dimension, par exemple l'épaisseur des particules est encore plus préférablement inférieure à 2 nm.As mentioned above, the composition can comprise a compound E consisting of small, dispersed particles. These are generally obtained from a compound having a structure in sheets. During the preparation of the composition, the sheets separate from each other so as to form the particles. The separation of the sheets is often called exfoliation, dissociation and delamination. The processes involved in this separation can be different depending on the compounds used and / or the processes used. They lead to obtaining particles with a higher or lower form factor whose small dimension is less than 10 nm. The small dimension, for example the thickness of the particles is even more preferably less than 2 nm.
Le composé à structure plaquettaire peut être choisi parmi plusieurs familles. On cite les fluoromicas, les phosphates de zirconium, les silicates, plus particulièrement les phyllosilicates, les hydrotalcites. On cite comme silicates plaquettaires convenables pour la mise en œuvre de l'invention les montmorillonites, smectites, illites, sépiolites, palygorkites, muscovites, ailervardites, amesites, hectorites, talcs, fluorohectorites, saponites, beidellites, nontronites, stevensites, bentonites, les micas, fluoromicas, vermicullites, fluorovermicullites, halloysites. Ces composés peuvent être d'origine naturelle, synthétique, ou naturelle modifiée. On préfère tout particulièrement les montmorillonites.The compound with a platelet structure can be chosen from several families. Mention is made of fluoromicas, zirconium phosphates, silicates, more particularly phyllosilicates, hydrotalcites. Mention is made, as platelet silicates suitable for the implementation of the invention, of montmorillonites, smectites, illites, sepiolite, palygorkites, muscovites, ailervardites, amesites, hectorites, talcs, fluorohectorites, saponites, beidellites, nontronites, stevensites, bentonites, micas , fluoromicas, vermicullites, fluorovermicullites, halloysites. These compounds can be of natural, synthetic, or modified natural origin. Particularly preferred are montmorillonites.
La séparation des feuillets en plaquettes (exfoliation, dissociation...) peut être favorisée par un traitement préalable à l'aide d'un composé organique, par exemple un composé organique permettant d'augmenter la distance entre les feuillets. La nature du traitement peut dépendre de la nature du composé à structure en feuillets. On cite à titre d'exemples les traitements par des ioniums, c'est à dire les ammoniums ou phosphoniums substitués, pour le traitement des montmorillonites. Des montmorillonites déjà traitées sont disponibles dans le commerce. De nombreux traitements et/ou procédés d'incorporation de composés à structure en feuillets dans des thermoplastiques, par exemple dans du polyamide, ont été décrits. Pour le traitement des montmorillonites, et éventuellement d'autres composés à structure en feuillets, on cite en particulier les traitements par échange de cations contenus initialement dans le composé. Il s'agit par exemple de cations organiques de type ioniums. Les cations organiques peuvent être choisis parmi les phosphoniums et les ammoniums, par exemple les ammoniums primaires à quaternaires. On peut citer par exemple les aminoacides protonés tels que l'acide 12-aminododecanoique protoné en ammonium, les aminés primaires à tertiaires protonées et les ammoniums quaternaires. Les chaînes attachées à l'atome d'azote ou de phosphore de l'onium peuvent être aliphatiques, aromatiques, arylaliphatiques, linéaires ou branchées et peuvent présenter des motifs oxygénés, par exemple des motifs hydroxy ou éthoxy. On peu citer à titre d'exemple de traitements organiques ammoniums le dodécyi ammonium, l'octadécyl ammonium, le bis(2-hydroxyethyl) octadécyl méthyl ammonium, le diméthyl dioctadécyl ammonium, l'octadécyl benzyl diméthyl ammonium, le tétraméthyl ammonium. On peut citer à titre d'exemple de traitements organiques phosphonium les alkyl phosphonium tels que le tétrabutyl phosphonium, le trioctyl octadécyl phosphonium, l'octadécyl triphényl phosphonium. Ces listes n'ont aucun caractère limitatif.The separation of the sheets into platelets (exfoliation, dissociation ...) can be favored by a preliminary treatment using an organic compound, for example an organic compound making it possible to increase the distance between the sheets. The nature of the treatment may depend on the nature of the compound with sheet structure. Examples of treatments by ioniums, that is to say substituted ammoniums or phosphoniums, for the treatment of montmorillonites are cited as examples. Montmorillonites already treated are commercially available. Numerous treatments and / or methods for incorporating compounds with a sheet structure in thermoplastics, for example in polyamide, have been described. For the treatment of montmorillonites, and possibly other compounds with a sheet structure, mention is made in particular of the treatments by cation exchange initially contained in the compound. These are, for example, organic cations of the ionium type. The organic cations can be chosen from phosphoniums and ammoniums, for example primary to quaternary ammoniums. Mention may be made, for example, of protonated amino acids such as protonated ammonium 12-aminododecanoic acid, protonated primary to tertiary amines and quaternary ammoniums. The chains attached to the nitrogen or phosphorus atom of onium can be aliphatic, aromatic, arylaliphatic, linear or branched and can have oxygenated units, for example hydroxy or ethoxy units. Examples of organic ammonium treatments that may be mentioned include dodecy ammonium, octadecyl ammonium, bis (2-hydroxyethyl) octadecyl methyl ammonium, dimethyl dioctadecyl ammonium, octadecyl benzyl dimethyl ammonium, tetramethyl ammonium. We can by way of example of organic phosphonium treatments, cite the alkyl phosphonium such as tetrabutyl phosphonium, trioctyl octadecyl phosphonium, octadecyl triphenyl phosphonium. These lists are in no way limiting.
Les silicates en feuillets convenables pour la réalisation de l'invention peuvent être choisis parmi les montmorillonites, smectites, illites, sépiolites, palygorkites, muscovites, allervardites, amesites, hectorites, talcs, fluorohectorites, saponites, beidellites, nontronites, stevensites, bentonites, les micas, fluoromicas, vermicullites, fluorovermicullites, halloysites. Ces composés peuvent être d'origine naturelle, synthétique, ou naturelle modifiée. Selon un mode de réalisation particulier de l'invention, les compositions sont composées de résine polyamide et de particules plaquettaires dispersées dans la résine, obtenues par exfoliation d'un phyllosilicate, par exemple une montmorillonite ayant subi préalablement un traitement de gonflement par échange d'ions. Des exemples de traitements gonflants pouvant être utilisés sont par exemple décrits dans le brevet EP 0398551. Tous les traitements connus pour favoriser l'exfoliation des phyllosilicates dans une matrice polymère peuvent être utilisés. On peut par exemple utiliser une argile traitée par un composé organique commercialisé par la société Laporte sous la marque Cloisite®. On peut également utiliser des argiles à base de montmorillonites commercialisées par la Société Nanocor sous la gamme Nanomer. Toute méthode permettant d'obtenir une dispersion de particules dans un polymère peut être utilisée pour mettre en œuvre l'invention. Un premier procédé consiste à mélanger le composé à structure en feuillets à disperser, éventuellement traité par exemple par un agent gonflant, dans le polymère fondu et à éventuellement soumettre le mélange à un cisaillement important, par exemple dans un dispositif d'extrusion bi-vis, afin de réaliser une bonne dispersion. Le polymère en question est entendu soit comme l'un des composés pris individuellement, de préférence du polyamide , soit comme le mélange des différents composés de la composition. Un autre procédé consiste à mélanger le composé à disperser, éventuellement traité par exemple par un agent gonflant, aux monomères dans le milieu de polymérisation, puis à polymériser. Dans ce cas le polymère est de préférence le polyamide. On introduit donc le composé plaquettaire éventuellement traité dans un milieu comprenant des monomères de polyamide puis on polymérise afin d'obtenir un polyamide (composé A) comprenant le composé E. Un autre procédé consiste à mélanger à un polymère fondu un mélange concentré d'un polymère et de particules dispersées, préparé par exemple selon l'un des procédés décrits précédemment. Les proportions en poids des différents composés sont de préférence les suivantes: Composé A: entre 5 et 95%, de préférence entre 30 et 70% Composé B: entre 5 et 95%, de préférence entre 20 et 40% Composé C: entre 0 et 30%, de préférence entre 5 et 20% Composé D: entre 0 et 30%, de préférence moins de 10%, par exemple entre 1 et 10%The sheet silicates suitable for carrying out the invention can be chosen from montmorillonites, smectites, illites, sepiolite, palygorkites, muscovites, allervardites, amesites, hectorites, talcs, fluorohectorites, saponites, beidellites, nontronites, stevensites, bentonites, micas, fluoromicas, vermicullites, fluorovermicullites, halloysites. These compounds can be of natural, synthetic, or modified natural origin. According to a particular embodiment of the invention, the compositions are composed of polyamide resin and platelet particles dispersed in the resin, obtained by exfoliation of a phyllosilicate, for example a montmorillonite having previously undergone a swelling treatment by exchange of ions. Examples of swelling treatments which can be used are for example described in patent EP 0398551. All the treatments known to promote the exfoliation of phyllosilicates in a polymer matrix can be used. It is possible, for example, to use a clay treated with an organic compound marketed by the company Laporte under the brand Cloisite®. It is also possible to use clays based on montmorillonites sold by the Nanocor Company under the Nanomer range. Any method making it possible to obtain a dispersion of particles in a polymer can be used to implement the invention. A first method consists in mixing the compound with a sheet structure to be dispersed, optionally treated for example with a swelling agent, in the molten polymer and optionally subjecting the mixture to significant shearing, for example in a twin-screw extrusion device , in order to achieve good dispersion. The polymer in question is understood either as one of the compounds taken individually, preferably polyamide, or as the mixture of the various compounds of the composition. Another method consists in mixing the compound to be dispersed, optionally treated for example with a swelling agent, with the monomers in the polymerization medium, then in polymerizing. In this case, the polymer is preferably polyamide. The platelet compound optionally treated is therefore introduced into a medium comprising polyamide monomers and then polymerized in order to obtain a polyamide (compound A) comprising compound E. Another method consists in mixing with a molten polymer a concentrated mixture of a polymer and dispersed particles, prepared for example by one of the methods described above. The proportions by weight of the various compounds are preferably as follows: Compound A: between 5 and 95%, preferably between 30 and 70% Compound B: between 5 and 95%, preferably between 20 and 40% Compound C: between 0 and 30%, preferably between 5 and 20% Compound D: between 0 and 30%, preferably less than 10%, for example between 1 and 10%
Dans le cas où la composition comprend un composé E, sa proportion en poids est avantageusement comprise entre 0,1 et 30%, de préférence entre 1 et 10%. Dans le cas où la composition comprend du polyamide 6, sa proportion en poids par rapport à la quantité totale de polyamide dans la composition est de préférence inférieure à 30%.In the case where the composition comprises a compound E, its proportion by weight is advantageously between 0.1 and 30%, preferably between 1 and 10%. In the case where the composition comprises polyamide 6, its proportion by weight relative to the total amount of polyamide in the composition is preferably less than 30%.
On détaille à présent des procédés pouvant être utilisés pour la préparation d'une composition selon l'invention.We now detail methods which can be used for the preparation of a composition according to the invention.
Les compositions thermoplastiques sont généralement obtenues par mélange des différents composés entrant dans la composition, les composés thermoplastiques étant sous forme fondue. On procède à plus ou moins haute température, à plus ou moins haute force de cisaillement selon la nature des différents composés. Les composés peuvent être introduits simultanément ou successivement. On utilise généralement un dispositif d'extrusion dans lequel la matière est chauffée, soumise à une force de cisaillement, et véhiculée. De tels dispositifs sont parfaitement connus de l'homme du métier.The thermoplastic compositions are generally obtained by mixing the various compounds entering into the composition, the thermoplastic compounds being in molten form. We proceed at more or less high temperature, at more or less high shear force depending on the nature of the different compounds. The compounds can be introduced simultaneously or successively. An extrusion device is generally used in which the material is heated, subjected to a shearing force, and conveyed. Such devices are perfectly known to those skilled in the art.
Selon un premier mode de réalisation, on mélange tous les composés en phase fondue au cours d'une unique opération, par exemple au cours d'une opération d'extrusion. On peut par exemple procéder à un mélange de granulés des matériaux polymériques, les introduire dans le dispositif d'extrusion afin de les fondre et de les soumettre à un cisaillement plus ou moins important. Dans le cas où un composé E est utilisé, ou généralement plus exactement un composé à structure piaquettaire traité formant des particules lors de la préparation de la composition, on préfère dans le cadre de ce procédé opérer sous un cisaillement relativement important afin de favoriser la dissociation des plaquettes.According to a first embodiment, all the compounds are mixed in the molten phase during a single operation, for example during an extrusion operation. It is possible, for example, to mix granules of polymeric materials, to introduce them into the extrusion device in order to melt them and subject them to more or less significant shearing. In the case where a compound E is used, or generally more exactly a compound with a piaquettary structure treated forming particles during the preparation of the composition, it is preferred in the context of this process to operate under relatively high shear in order to promote dissociation platelets.
On peut, selon des modes de réalisations particuliers, effectuer des pré-mélanges de certains des composés avant préparation de la composition finale. Par exemple dans le cas où la composition comprend un composé E, le procédé de fabrication de la composition peut comprendre les opérations suivantes: a) préparation d'un matériau composite comprenant du polyamide et le composé E b) mélange en phase fondue du matériau composite, des autres composés et le cas échéant de polyamide ne comprenant pas de composé E.It is possible, according to particular embodiments, to pre-mix certain of the compounds before preparation of the final composition. For example, in the case where the composition comprises a compound E, the process for manufacturing the composition can comprise the following operations: a) preparation of a composite material comprising polyamide and the compound E b) mixing in the molten phase of the composite material, of the other compounds and, where appropriate, of polyamide not comprising compound E.
Le matériau composite préparé à l'étape a) peut être obtenu par l'un des procédés suivants: polymérisation de polyamide en présence du composé E sous forme de particules ou d'un composé à structure en feuillets éventuellement traité. Dans le cadre d'un tel processus, le polyamide ainsi préparé est de préférence à base de polyamide 6, les monomères étant principalement choisis parmi le caprolactame et/ou l'acide 6-amino-caproïque. mélange en phase fondue de polyamide et du composé E sous forme de particules ou d'un composé à structure en feuillets éventuellement traité. Le mélange peut être effectué à l'aide d'un dispositif d'extrusion, de préférence à cisaillement important. Le matériau composite obtenu à l'étape a) constitue un pré-mélange. Il sera mélangé en phase fondue aux autres composés au cours d'un opération b), par exemple à l'aide d'un dispositif d'extrusion, comme décrit précédemment. Au cours de cette opération b), on peut ajouter du polyamide ne comprenant pas le composé E. Le polyamide constituant le composé A compris dans la composition provient alors du polyamide du matériau composite, et du polyamide ajouté lors de l'opération b).The composite material prepared in step a) can be obtained by one of the following methods: polymerization of polyamide in the presence of compound E in the form of particles or of a compound with a sheet structure optionally treated. Within the framework of such a process, the polyamide thus prepared is preferably based on polyamide 6, the monomers being mainly chosen from caprolactam and / or 6-amino-caproic acid. melt-blending of polyamide and of compound E in the form of particles or of a compound with a sheet structure possibly treated. The mixing can be carried out using an extrusion device, preferably with high shear. The composite material obtained in step a) constitutes a premix. It will be mixed in the molten phase with the other compounds during an operation b), for example using an extrusion device, as described above. During this operation b), it is possible to add polyamide not comprising the compound E. The polyamide constituting the compound A included in the composition then comes from the polyamide of the composite material, and from the polyamide added during operation b).
La composition selon l'invention, lorsqu'elle est préparée à l'aide d'un dispositif d'extrusion est de préférence conditionnée sous forme de granulés.The composition according to the invention, when it is prepared using an extrusion device, is preferably packaged in the form of granules.
Elle, ou généralement plus précisément les granulés, est destinée à être mise en forme à l'aide de procédés impliquant une fusion pour l'obtention d'articles. Les articles sont ainsi constitués de la composition.It, or generally more precisely the granules, is intended to be shaped using methods involving a fusion to obtain articles. The articles are thus made up of the composition.
L'utilisation des compositions selon l'invention est particulièrement intéressante dans le cadre de la fabrication d'articles pour l'industrie automobile, en particulier pour la fabrication de pièces de carrosserie.The use of the compositions according to the invention is particularly advantageous in the context of the manufacture of articles for the automotive industry, in particular for the manufacture of body parts.
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 appear more clearly in the light of the examples given below only for information.
Composés utilisés - Composé A1 : Polyamide 66, de viscosité relative de 2,90, comprenant 55 meq/kg de groupement terminaux aminés et 40 meq/kg de groupements terminaux acides, commercialisé par la société Rhodia Engineering Plastics sous la référence Technyl 29 AP NH.Compounds used - Compound A1: Polyamide 66, with a relative viscosity of 2.90, comprising 55 meq / kg of amino end groups and 40 meq / kg of acid end groups, marketed by Rhodia Engineering Plastics under the reference Technyl 29 AP NH.
- Composé A2: Polyamide 6, de viscosité relative de 3,0, commercialisé par la société Hyosung Corporation sous la référence Toplamid 1021. - Composé A3 : Polyamide 66, d'indice de viscosité dans l'acide formique à 88% de 126, commercialisé par la société Rhodia Engineering Plastics sous la référence Technyl 27A- Compound A2: Polyamide 6, with a relative viscosity of 3.0, sold by the company Hyosung Corporation under the reference Toplamid 1021. - Compound A3: Polyamide 66, with a viscosity index in 88% formic acid of 126, marketed by Rhodia Engineering Plastics under the reference Technyl 27A
- Composé B1: Copolymère Acrylonitrile-Butadiène-Styrène commercialisé par la société BASF Korea sous la référence Terluran EHI-5. - Composé B2: Copolymère Acrylonitrile-Butadiène-Styrène commercialisé par la société BASF sous la référence Terluran KR 2910- Compound B1: Acrylonitrile-Butadiene-Styrene copolymer marketed by BASF Korea under the reference Terluran EHI-5. - Compound B2: Acrylonitrile-Butadiene-Styrene copolymer sold by BASF under the reference Terluran KR 2910
- Composé C1: Copolymère Styrène-Maléimide (N-phénylmaléimide) greffé anhydride maléique, comprenant 46% en poids de Styrène, 53% en poids de N- phénylmaléimide, 1% en poids d'anhydride maléique, commercialisé par la société Nippon Shokubaï sous la référence PSX 0371.- Compound C1: Styrene-Maleimide (N-phenylmaleimide) copolymer grafted with maleic anhydride, comprising 46% by weight of Styrene, 53% by weight of N-phenylmaleimide, 1% by weight of maleic anhydride, sold by the company Nippon Shokubaï under the reference PSX 0371.
- Composé C2: Styrène-Etylène-Butylène-Styrène hydrogéné (SEBS) greffé anhydride maléique commercialisé par la société commercialisé par la société Shell sous la référence FG1901X- Compound C2: Styrene-Etylene-Butylene-Hydrogenated styrene (SEBS) grafted maleic anhydride marketed by the company marketed by the company Shell under the reference FG1901X
Composé D1 : Elastomère Ethylène-Propylène greffé anhydride maléique commercialisé par la société Mitsui Chemical sous la référence MP 0620.Compound D1: Ethylene-Propylene elastomer grafted with maleic anhydride sold by the company Mitsui Chemical under the reference MP 0620.
- Composé F1 : Lubrifiants, Noir de carbone, Nigrosine- F1 compound: Lubricants, Carbon black, Nigrosine
Préparation des compositionsPreparation of the compositions
Les compositions ont été préparées par mélange en phase fondue à l'aide d'une extrudeuse bi-vis de type WERNER et PFLEIDERER ZSK. Les conditions d'extrusion étaient les suivantes:The compositions were prepared by mixing in the melt phase using a twin-screw extruder of the WERNER and PFLEIDERER ZSK type. The extrusion conditions were as follows:
- Température: entre 240 et 280°C- Temperature: between 240 and 280 ° C
- Vitesse de rotation: entre 200 et 300 tours/min- Rotation speed: between 200 and 300 rpm
- Débit entre 25 et 30 kg/heure Exemples 1 à 3- Flow between 25 and 30 kg / hour Examples 1 to 3
Les différentes compositions préparées sont présentées en tableauThe different compositions prepared are presented in table
Tableau ITable I
Figure imgf000015_0001
Figure imgf000015_0001
Les compositions obtenues présentent une excellente compatibilisation entre le polyamide et l'acrylonitrile-butadiène-styrène, des propriétés mécaniques et/ou un aspect de surface amélioré par rapport à des compositions obtenues à partir d'un polyamide 66 dont les quantités de groupements terminaux aminés et acides sont équilibrées, ou qui comportent plus de groupement terminaux acides que de groupements terminaux aminés.The compositions obtained have excellent compatibilization between the polyamide and acrylonitrile-butadiene-styrene, mechanical properties and / or an improved surface appearance compared to compositions obtained from a polyamide 66, the amounts of terminal amino groups and acids are balanced, or which contain more acidic end groups than amino end groups.
Exemples 4 et 5Examples 4 and 5
Les différentes compositions préparées sont présentées en tableau II.The various compositions prepared are presented in Table II.
EvaluationsEvaluations
Différents tests ont été effectués sur les compositions:Different tests were carried out on the compositions:
Contrainte au seuil de plasticité selon la norme ISO 527Stress at the plasticity threshold according to ISO 527 standard
Contrainte à la rupture selon la norme ISO 527,Breaking stress according to ISO 527,
Elongation à la rupture selon la norme ISO 527,Elongation at break according to ISO 527,
- Module de traction selon la norme ISO 527- Traction module according to ISO 527 standard
- Résistance aux chocs Izod entaillé selon la norme ISO 180/1 A, mesuré à 23°C, sous un impact de 4t.- Izod impact resistance notched according to ISO 180/1 A, measured at 23 ° C, under an impact of 4t.
- Résistance aux chocs Charpy entaillé selon la norme ISO 179/1eA, mesuré à 23°C, sous un impact de 4t.- Impact resistance Charpy notched according to ISO 179 / 1eA, measured at 23 ° C, under an impact of 4t.
- Température de déformation sous charge (HDT - Heat deflection température) selon la norme ISO 75B, sous charge de 0,45 MPa Tableau II- Deformation temperature under load (HDT - Heat deflection temperature) according to ISO 75B, under load of 0.45 MPa Table II
Figure imgf000016_0001
Figure imgf000016_0001
Les évaluations des compositions sont présentées en tableau IIIThe evaluations of the compositions are presented in Table III
Tableau IIITable III
Figure imgf000016_0002
Figure imgf000016_0002
Les compositions obtenues présentent une excellente compatibilisation entre le polyamide et l'acrylonitrile-butadiène-styrène, des propriétés mécaniques et/ou un aspect de surface amélioré par rapport à des compositions obtenues à partir d'un polyamide 66 dont les quantités de groupements terminaux aminés et acides sont équilibrées. The compositions obtained have excellent compatibilization between the polyamide and acrylonitrile-butadiene-styrene, mechanical properties and / or an improved surface appearance compared to compositions obtained from a polyamide 66, the amounts of terminal amino groups and acids are balanced.

Claims

REVENDICATIONS
1. Composition thermoplastique comprenant les composés suivants:1. Thermoplastic composition comprising the following compounds:
Composé A: polyamide thermoplastique du type de ceux obtenus à partir de diacides et de diamines, la quantité de groupements terminaux aminés étant supérieure à la quantité de groupements terminaux acides. Composé B: copolymère comprenant un caoutchouc sur lequel sont greffés de l'acryionitrile et un composé styrenique choisi parmi le styrène et l'α-méthyle-styrène, le copolymère comprenant le cas échéant des groupements fonctionnels de compatibilisation avec le polyamide,Compound A: thermoplastic polyamide of the type of those obtained from diacids and diamines, the quantity of amino terminal groups being greater than the quantity of acid terminal groups. Compound B: copolymer comprising a rubber onto which are grafted acrylonitrile and a styrenic compound chosen from styrene and α-methyl-styrene, the copolymer comprising, where appropriate, functional groups for compatibilization with the polyamide,
Composé C: le cas échéant un ou plusieurs agent de compatibilisation entre le polyamide et le composé B, dont au moins un comprend des groupements fonctionnels de compatibilisation avec le polyamide Composé D: le cas échéant un composé élastomérique, la composition comprenant au moins un composé comprenant des groupements fonctionnels de compatibilisation avec le polyamide.Compound C: where appropriate one or more compatibilizing agent between the polyamide and the compound B, at least one of which comprises functional groups for compatibilization with the polyamide Compound D: where appropriate an elastomeric compound, the composition comprising at least one compound comprising functional groups for compatibilization with the polyamide.
2. Composition selon la revendication 1 caractérisée en ce que le polyamide constitue une matrice à l'intérieur de laquelle sont dispersés des nodules du composé B.2. Composition according to claim 1 characterized in that the polyamide constitutes a matrix inside which are dispersed nodules of compound B.
3. Composition selon l'une des revendications précédentes caractérisée en ce que le composé A est un polyamide 66, obtenu à partir d'acide adipique et d'hexaméthylène diamine.3. Composition according to one of the preceding claims, characterized in that the compound A is a polyamide 66, obtained from adipic acid and hexamethylene diamine.
4. Composition selon l'une des revendications précédentes caractérisée en ce que la quantité de groupements terminaux aminés est supérieure à 50 meq/kg et en ce que la différence entre les quantités de groupements terminaux aminés et de groupements terminaux acides est supérieure à 5 meq/kg.4. Composition according to one of the preceding claims, characterized in that the quantity of amino terminal groups is greater than 50 meq / kg and in that the difference between the quantities of amino terminal groups and of acid terminal groups is greater than 5 meq / kg.
5. Composition selon l'une des revendications précédentes caractérisée en ce que le composé B est un copolymère à base d'Acryloninitrile-Butadiène-Styrène, comprenant le cas échéant des fonctions de compatibilisation avec le polyamide5. Composition according to one of the preceding claims, characterized in that the compound B is a copolymer based on Acryloninitrile-Butadiene-Styrene, optionally comprising compatibilization functions with the polyamide
6. Composition selon l'une des revendications précédentes caractérisée en ce que le composé C est choisi parmi les copolymères styrène-maléimide comprenant des groupements fonctionnels de compatibilisation avec le polyamide, les copolymères block Styrène-Ethylène-Butadiène-Styrène ou Styrène-Butadiène-Styrène le cas échéant totalement ou partiellement hydrogénés, présentant des groupements fonctionnels de compatibilisation avec le polyamide.6. Composition according to one of the preceding claims, characterized in that the compound C is chosen from styrene-maleimide copolymers comprising functional groups for compatibilization with the polyamide, the copolymers Styrene-Ethylene-Butadiene-Styrene or Styrene-Butadiene-Styrene block, where appropriate totally or partially hydrogenated, having functional groups for compatibilization with the polyamide.
7. Composition selon l'une des revendications précédentes caractérisée en ce que les groupements fonctionnels de compatibilisation avec le polyamide sont choisis parmi les groupements anhydride maléique, acide carboxylique, ester.7. Composition according to one of the preceding claims, characterized in that the functional groups for compatibilization with the polyamide are chosen from maleic anhydride, carboxylic acid and ester groups.
8. Composition selon l'une des revendications précédentes caractérisée en ce que les proportions en poids des différents composés sont les suivantes:8. Composition according to one of the preceding claims, characterized in that the proportions by weight of the various compounds are as follows:
Composé A: entre 5 et 95% Composé B: entre 5 et 95% Composé C: entre 0 et 30%> Composé D: entre 0 et 30%Compound A: between 5 and 95% Compound B: between 5 and 95% Compound C: between 0 and 30%> Compound D: between 0 and 30%
9. Composition selon l'une des revendications précédentes caractérisée en ce que les proportions en poids des différents composés sont les suivantes:9. Composition according to one of the preceding claims, characterized in that the proportions by weight of the different compounds are as follows:
Composé A: entre 30 à 70% Composé B: entre 20 et 40% Composé C: entre 5 et 20%Compound A: between 30 to 70% Compound B: between 20 and 40% Compound C: between 5 and 20%
Composé D: entre 1 et 10%Compound D: between 1 and 10%
10. Composition selon l'une des revendications précédentes caractérisée en ce que le composé D est choisi parmi les caoutchouc Ethylène-Propylène greffés par de l'anhydride maléique.10. Composition according to one of the preceding claims, characterized in that the compound D is chosen from Ethylene-Propylene rubbers grafted with maleic anhydride.
11. Composition selon l'une des revendications précédentes caractérisée en ce qu'elle comprend un composé à base de polyamide 6.11. Composition according to one of the preceding claims, characterized in that it comprises a compound based on polyamide 6.
12. Composition selon la revendication précédente caractérisée en ce que la proportion en poids du composé à base de polyamide 6 est inférieure à 30% par rapport à la quantité totale de polyamide dans la composition.12. Composition according to the preceding claim, characterized in that the proportion by weight of the compound based on polyamide 6 is less than 30% relative to the total amount of polyamide in the composition.
13. Procédé de fabrication d'une composition selon l'une des revendications précédentes caractérisé en ce qu'il consiste à mélanger les composés en phase fondue. 13. A method of manufacturing a composition according to one of the preceding claims characterized in that it consists in mixing the compounds in the molten phase.
14. Articles mis en forme constitués d'une composition selon l'une des revendications précédentes.14. Shaped articles consisting of a composition according to one of the preceding claims.
15. Utilisation d'une composition selon l'une des revendications 1 à 13 pour la fabrication de pièces de carrosserie automobile. 15. Use of a composition according to one of claims 1 to 13 for the manufacture of automobile body parts.
PCT/EP2002/001632 2001-02-16 2002-02-15 Thermoplastic polymer composition based on polyamide WO2002066557A1 (en)

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