FR2833603A1 - Thermoplastic polymer composition, used e.g. for production of moulded products, film or fibres, contains a functionalised, hyper-branched copolyamide as rheology modifier - Google Patents

Abstract

Functionalised, hyper-branched copolyamides are used as rheology modifiers in thermoplastic polymer compositions. A thermoplastic polymer composition (TPC) comprising a thermoplastic polymer-based matrix (M) and rheology-modifying additive(s) (PAHB) consisting of functionalised, hyperbranched copolyamide(s) obtained by reaction of (a) monomer(s) of formula A-R-Bf (I), possibly (b) difunctional spacer monomer(s) of formula A'-R'-B' (II) or the corresponding lactams, possibly (c) core monomer(s) of formula R<1>(B)n (III) and (d) chain-regulating monomer(s) of formula R<2>-A (IV), at least 50% of the terminal groups in the copolyamide being functionalised by R<2>. A, A', A = reactive polymer-forming groups; B, B', B = polymer-forming groups which react with A, A' or A; R, R' = hydrocarbon units, optionally with hetero-atoms; f = at least 2, preferably 2-10; R<1>, R<2> = optionally substituted hydrocarbon groups such as silicone, linear or branched alkyl, aryl, alkylaryl, aralkyl or cycloaliphatic groups (optionally unsaturated and/or with hetero-atoms); n = 1 or more, preferably 1-100 An Independent claim is also included for articles obtained by forming TPC, preferably by moulding, compression moulding, injection blow moulding, extrusion blow moulding, extrusion or spinning.

Description

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Thermoplastic polymer composition comprising a hyperbranched copolyamide, and articles made from this composition
The field of the invention is that of thermoplastic polymer compositions comprising a thermoplastic polymer matrix and at least one additive modifying the rheological behavior.

For the purposes of the present disclosure, the term “polymer” denotes both a homopolymer and a copolymer.

Thermoplastic polymers are raw materials capable of being transformed by molding, injection molding, injection blow molding, extrusion, extrusion / blow molding or spinning, in particular into multiple articles such as parts (for example for bodywork) blown, extruded, or molds, threads, fibers or films ...

There are at least two major constraints in all these thermoplastic polymer transformation routes.

The first of these constraints is that the thermoplastic polymers used must be characterized, in the molten state, by a viscosity or a rheological behavior compatible with the shaping processes referred to above. These thermoplastic polymers must be sufficiently fluid when they are molten, to be able to be conveyed and handled easily and quickly in certain forming machines.

The other constraint which weighs on thermoplastic polymer compositions is linked to the mechanical qualities which they must exhibit after having been melted, shaped and hardened by cooling. These mechanical qualities are in particular impact resistance, flexural modulus, flexural stress at break, among others.

Moreover, in order to improve the mechanical properties of thermoplastic polymers, it is common practice to add reinforcing fillers (fibers or threads) to them, for example, mineral, glass or carbon, to form composite materials.

One of the technical problems posed with regard to these two constraints: rheological behavior in the molten state and mechanical properties of the shaped product and in the solidified state, is that they are a priori contradictory.

In fact, in order to reduce the viscosity in the molten state, it is well known to select thermoplastic polymers having low molar masses. But this gain in terms of rheology comes at the expense of the mechanical qualities of the shaped and hardened polymer.

In an attempt to correct this, it is also common practice to incorporate into thermoplastic polymer matrices various additives capable of modifying their

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rheological behavior in the molten state. These additives are all the more useful when the polymers include reinforcing fillers.

The dilemma we face with these additives is that they must be both inert or non-reactive with the matrix so as not to induce profound changes in the chemical structure (for example crosslinking), while being dispersible in this matrix for provide it with the required functionalities, in a consistent manner.

However, the first requirement of non-reactivity would rather tend to refer to additive molecules not compatible with those of the matrix, while the second requirement of dispersibility rather directs those skilled in the art towards additives with a structure compatible with the matrix. that of the matrix.

Moreover, the additives modifying the rheology must be able to improve the capacity of the thermoplastic polymer and to be molded, injected or extruded.

As regards the polyamides which are of more particular interest in the context of the present invention, it has been proposed to use hyperbranched copolyamides as rheology modifying additives in thermoplastic polyamide matrices.

The French patent application? 2 793 252 describes hyperbranched copolyamides (PAHB), for example of the type of those with carboxylic acid terminations, obtained by molten phase copolycondensation of 1,3,5-benzene tricarboxylic acid (BTC): core molecule of Rl-B type "3, with B" = COOH, of 5-aminoisophthalic acid (AIPA): branching molecule of type AR-B2, with A = NH2 and B = COOH and of s - caprolactam (CL): spacer of type A '-R'-B' with A '= NH2 and B' = COOH).

PAHBs generally have a size varying from a few nanometers to several tens of nanometers.

These hyperbranched polyamides can be functionalized in particular by fatty chains or hydrophobic and / or hydrophilic chains, for the purposes of being used, for example, as an agent for modifying the surface properties of the polyamide, for linear or branched polymers, preferably polyamides. These functionalities can be provided on the hyperbranched polyamide by involving in the molten phase copolycondensation, an R "'- A type chain stopper monomer.

In this state of the art, one of the essential objectives of the present invention is to provide an additive for modifying the rheological behavior of thermoplastic polymers which is:

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- capable of allowing the controlled modification of the rheological properties of the thermoplastic composition, in particular the viscosity in the molten state (fluidization), and this without affecting the mechanical properties of the shaped and hardened thermoplastic polymer (impact resistance), - Preferably non-reactive with respect to the thermoplastic matrix, advantageously made of polyamide, that is to say not capable of causing changes in chemical structure on the thermoplastic matrix, resulting for example in decreases in the molar mass of the matrix, - preferably easily dispersible in this matrix.

Another objective of the invention is to provide a thermoplastic polymer composition comprising a thermoplastic matrix and at least one additive chosen from modifiers of the rheological behavior in the molten state, such that the composition has a fluidity in the molten state. suitable for molding and injection operations (complete filling of the mold), without compromising mechanical properties, and in particular impact resistance.

Another objective of the present invention is to provide a thermoplastic polymer composition suitable for the various forming techniques in the molten state: injection molding, injection / blow molding, extrusion / blow molding, filming, extrusion, spinning, moreover having a high mechanical strength and possibly good transparency (low crystallinity).

Another objective of the invention is to provide a thermoplastic polymer composition having the rheological (in the molten state) and mechanical qualities required in the plastics processing industry, without the admixture carried out for the improvement of these properties. is too expensive and disrupts the other properties of thermoplastics.

Another objective of the invention is to provide a PAHB additive modifying the rheological behavior capable of modifying in a controlled and optimized manner the rheological behavior in the molten state of thermoplastic polymer compositions.

Another essential objective of the invention is to provide articles obtained by processing (molding, injection molding, injection / blow molding, extrusion / blow molding, extrusion or spinning) of the composition as defined in the above objectives.

These objectives, among others, are achieved by the present invention which results from the judicious and advantageous selection that the inventors have had the merit of making, by retaining specific PAHBs as modifying additive of the rheological behavior in the molten state.

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ci-dessus respectivement pour A, B, R dans la formule (I) ; éventuellement au moins un monomère "creur" de formu1e (III) : (III) R\B") n * dans laquelle : * R 1 est un radical hydrocarboné substitué ou non, du genre silicone, alkyle linéaire ou ramifié, aromatique, alkylaryle, arylalkyle ou cycloaliphatique pouvant comprendre des insaturations et/ou des hétéroatomes ; * B" est une fonction réactive de même nature que B ou B' ; * n > 1, de préférence ln 100 . et au moins un monomère de fonctionnalisation"limiteur de chaîne" répondant à la formule (IV) : (IV) R2 -A" From which it follows that the present invention relates firstly to a thermoplastic polymer composition characterized in that it comprises: # a matrix M based on at least one thermoplastic polymer, # and at least one PAHB additive modifying the rheological behavior comprising at least one copolyamide: # functionalized, # hyperbranched of the type of those obtained by reaction between: a at least one monomer of the following formula (1): (I) AR-Bf in which A is a reactive polymerization function d 'a first type, B is a reactive polymerization function of a second type and capable of reacting with A, R is a hydrocarbon entity optionally comprising heteroatoms, and f is the total number of reactive functions B per monomer: f # 2 , preferably 2::; f::; 10; optionally at least one bifunctional spacer monomer of the following formula (II): (II) A'-R'-B 'or the corresponding lactams, in which A', B ', R' have the same definition as that given

above respectively for A, B, R in formula (I); optionally at least one "creur" monomer of formula (III): (III) R \ B ") n * in which: * R 1 is a substituted or unsubstituted hydrocarbon radical, of the silicone, linear or branched alkyl, aromatic or alkylaryl type , arylalkyl or cycloaliphatic which may comprise unsaturations and / or heteroatoms; * B "is a reactive function of the same nature as B or B '; * n> 1, preferably ln 100. and at least one "chain-limiting" functionalization monomer corresponding to formula (IV): (IV) R2 -A "

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in which: + R2 is a substituted or unsubstituted hydrocarbon radical of the silicone, linear or branched alkyl, aromatic, arylalkyl, alkylaryl or cycloaliphatic type which may comprise one or more unsaturations and / or one or more heteroatoms,. and A "is a reactive function of the same nature as A or A '; at least 50% of the end groups of this hyperbranched copolyamide are functionalized with R2.

Preferably, the composition according to the invention is free from PAHB additives resulting in a reduction in the molar mass of the matrix M of greater than or equal to 7% relative to a control composition comprising the same matrix M not supplemented with PAHB, the molar mass measurement being carried out according to a determined P protocol. The detail of the protocol P for measuring the molar mass is given in the examples below.

In accordance with the invention, the functionalized PAHB additive therefore has the advantageous essential characteristic of an ability to modify the rheological behavior of a thermoplastic polymer matrix, without impairing its structural integrity, and in particular without significantly reducing its mass. molar.

This means that the additive does not seem to react with the matrix.

According to the present invention, the molar mass is defined as the maximum of the distribution of the molar masses of the polyamide matrix supplemented with functionalized PAHB, in polystyrene equivalent, by gel permeation chromatography (GPC), in detection by refractometry, as is defined in protocol P given in detail below.

The molar mass measurement is carried out on the composition to be analyzed and on the control composition, extruded, solidified and then optionally placed in the form of granules.

The above-mentioned protocol P for measuring the molar mass of the matrix M in a composition to be analyzed and in a control composition involves extrusion, which leads to the production of rods. The rods (previously cut into granules) are then subjected to the determination of the actual molar mass. This protocol P for measuring the molar mass of the compositions according to the invention and of the control compositions is as follows:

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11 Matrix M / Functionalized PAHB Compositions The (co) polyamide matrix M and the functionalized PAHB are in the form of ground or crushed powder, flakes or granules, and are then premixed.

The mixture is introduced into a twin-screw extruder.

This mixture is melted in the extruder at a temperature Q of about 30 ° C. above the melting temperature Fus. on of the matrix M.

The homogenization of M / PAHB is thus carried out for 5 min and rods are collected at the extruder outlet which are then placed in the form of granules.

The actual molar mass measurement is carried out on the granules by gel permeation chromatography (GPC) in dichloromethane after derivatization of the polyamide with trifluoroacetic anhydride, relative to polystyrene standards. The detection technique used is refractometry.

2 / Matrix control compositions. M without PAHB additive For each given M / PAHB composition, a molar mass measurement of the same matrix M is carried out on a composition comprising the matrix M without PAHB additive.

The method is carried out on copolyamide M granules obtained in the same way as that indicated in point 1 above, with the difference that the granules do not contain any PAHB additive.

As regards the M + functionalized PAHB composition of the invention, it may be noted that extrusion constitutes one means, among others, of mixing in the molten state the constituents M and functionalized PAHB.

The radical R 2 for functionalizing the PAHB is preferably non-reactive with the matrix and, quite surprisingly and unexpectedly, induces a very significant fluidification of the composition in the molten state. Indeed, the gains obtained in this regard are particularly important since they can be for example at least 10 to 50%, without this altering the mechanical properties, and in particular the impact resistance of the thermoplastic.

The fluidity / impact resistance compromise achieved is quite interesting.

The functionalized PAHB additive used in accordance with the invention is easy to use and economical.

According to a preferred arrangement of the invention, the functionalized PAHB additive of the composition is characterized in that: the hydrocarbon entities R, R ′ of the monomers (1) and (II) respectively, each comprise:

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i. at least one linear or branched aliphatic radical; ii. and / or at least one cycloaliphatic radical; iii. and / or at least one aromatic radical comprising one or more aromatic rings; iv. and / or at least one arylaliphatic radical; these radicals (i), (ii), (iii), (iv) possibly being substituted and / or comprising heteroatoms;
A, A ′ is a reactive function of the amine, amine salt or acid, ester, acid halide or amide type;
B, B ′ is a reactive function of the acid, ester, acid halide or amide type or of the amine or amine salt type.

Thus, the reactive polymerization functions A, B, A ′, B ′ more especially selected are those belonging to the group comprising the carboxylic and amine functions.

For the purposes of the invention, the term “carboxylic function” is understood to mean any COOH or derivative acid function, in particular of the ester or anhydride, acid halide (chloride) type.

Advantageously, the PAHB modifying the rheological behavior in the composition according to the invention can consist of a mixture of several different monomers (1), of several different monomers (II), and / or of several monomers (IV) of different functionalization. .

Bifunctional monomers (II) are spacers in the three-dimensional structure.

According to an advantageous embodiment of the invention, the spacer monomers (II), the chain-limiting monomers (IV), and / or the “core” type monomers (III) can be in the form of oligomers.

Preferably, f = 2 so that the monomer (1) is trifunctional: A-R-B2, A = amine function, B = carboxylic function and R = aromatic radical.

Furthermore, it is preferable that the functionalized PAHB additive is characterized by a molar ratio III / 1 + II + IV being defined as follows: III / I + II + IV 1/150 and preferably III / 1 + II + IV 1/100 and more preferably still III / 1 + II + IV 1/50
According to a particular feature of the invention, the functionalized PAHB additive used is, for example: - either "small" (of low mass), that is to say characterized by a ratio: 1 / 10III / I + II + IV 1/40,

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- either "large" (of high mass), ie characterized by a ratio: 1/50 III / I + II + IV 1/90.

According to an advantageous variant, the radical R2 for functionalizing the PAHB is chosen from linear alkyls comprising from 8 to 30 carbon atoms, preferably from 10 to 20 carbon atoms, or polycondensed or non-polycondensed aryls, arylalkyls or alkylaryls.

- l'acide amino-11-undécanoïque, - le lauryllactame et/ou l'aminoacide correspondant, - l'acide amino-12-dodécanoïque - et leurs mélanges ; * le monomère"coeur" (III) est choisi dans le groupe comprenant : - l'acide 1,3, 5-benzène tricarboxylique, - la 2,2, 6, 6-tétra- (P-carboxyéthyl) cyclohexanone,

- la 2, 4, 6-tri- (acide aminocaproïque)-1, 3, 5-triazine, - la 4-aminoéthyl-1, 8-octanediamine, - et leurs mélanges ; . 1e monomère de fonctionnalisation"limiteur de chaîne" (IV) est choisi dans le groupe comprenant : - la n-hexadécylamine, - la n-octadécylamine, - la n-dodécylamine, In practice, and without this being limiting for the functionalized PAHB: e the monomer (1) is chosen from the group comprising: - 5-amino-isophthalic acid, - 6-amino-undecandioic acid, - 3-aminopimelic acid, - aspartic acid, - 3,5-diaminobenzoic acid, - 3,4-diaminobenzoic acid, - and mixtures thereof; the bifunctional monomer of formula (II) is chosen from the group comprising: - # - caprolactam and / or the corresponding amino acid: aminocaproic acid, - para or metaaminobenzoic acid,

- 11-amino-undecanoic acid, - lauryllactam and / or the corresponding amino acid, - 12-amino-dodecanoic acid - and mixtures thereof; * the “core” monomer (III) is chosen from the group comprising: - 1,3,5-benzene tricarboxylic acid, - 2,2, 6, 6-tetra- (P-carboxyethyl) cyclohexanone,

- 2, 4, 6-tri- (aminocaproic acid) -1, 3, 5-triazine, - 4-aminoethyl-1, 8-octanediamine, - and mixtures thereof; . The “chain stopper” functionalizing monomer (IV) is chosen from the group comprising: - n-hexadecylamine, - n-octadecylamine, - n-dodecylamine,

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- benzylamine, - and mixtures thereof.

For more details on this PAHB, we refer to the French patent application? 2,793,252, both as regards the structural aspects and the methods of obtaining this functionalized PAHB.

As regards the monomers (1), (II) and optionally (III), there will be mentioned respectively 5-aminoisophthalic acid (AIPA, branching molecule of AR'-B2 type, with A = NH2), caprolactam (noted CL, AR type spacer "-B) and 1,3,5-benzene tricarboxylic acid (BTC, R-B3 type core molecule, with B = COOH).

From a quantitative standpoint, it is preferable in the context of the invention for the additive comprising the hyperbranched copolymer to be present in an amount of (in% by dry weight relative to the total mass of the composition):

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<tb> 0, <SEP> 1 <SEP> to <SEP> 50
<tb> from <SEP> preference <SEP> 1 <SEP> to <SEP> 20
<tb> and <SEP> plus <SEP> preferably <SEP> again <SEP> 2 <SEP> to <SEP> 10.
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In addition, it has turned out to be particularly advantageous that the functionalized PAHB and used as additive modifying the rheological behavior in the composition according to the invention, that is to say a PAHB whose content of acid or amine end groups (GT) (expressed in meq / kg) between 0 and 100, preferably between 0 and 50, and more preferably still between 0 and 25.

The manufacture of a functionalized hyperbranched copolyamide of the type of that referred to above, namely: 0 consisting of one or more functionalized tree structures, via monomers (IV) carrying the functionalities considered, 0 and of the type of those obtained by reaction between:. at least one monomer of formula (I) below: (1) AR-Bf in which A is a reactive polymerization function of a first type, B is a reactive polymerization function of a second type and capable of reacting with A , R is a hydrocarbon entity optionally comprising heteroatoms, and f is the total number of reactive functions B per monomer: f 2, preferably 2 <f <10;

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+ optionally at least one bifunctional monomer of the following formula (II): (II) A'-R'-B 'or the corresponding lactams, in which A', B ', R' have the same definition as that given above respectively for A, B, R in formula (1); . optionally at least one "core" monomer of formula (III): (III) R '(B "), in which: - is a substituted or unsubstituted hydrocarbon radical, of the silicone, linear or branched alkyl, aromatic, alkylaryl or arylalkyl type or cycloaliphatic which may comprise unsaturations and / or heteroatoms; - B "is a reactive function of the same nature as B or B '; - nose 1, preferably 1 n 100 and at least one "chain-limiting" functionalizing monomer corresponding to formula (IV): (IV) RA "in which: - R2 is a substituted or unsubstituted hydrocarbon radical, of the silicone type , linear or branched alkyl, aromatic, arylalkyl, alkylaryl or cycloaliphatic which may comprise one or more unsaturations and / or one or more heteroatoms; and A "is a reactive function of the same nature as A or A '; is carried out by melt-phase polycondensation between monomers (I), optionally monomers (II), which also react with each other and with functionalizing monomers (IV), and optionally with monomers (III).

The polymerization by copolycondensation is carried out, for example, under conditions and according to a procedure equivalent to those used for the manufacture of linear polyamides, for example from monomers (II).

Concerning the essential constituent from the quantitative point of view of the composition according to the invention, namely the thermoplastic matrix, the thermoplastic (co) polymer (s) constituting the matrix is (are) chosen from the group comprising: polyolefins, polyesters, polyalkylene oxides, polyoxyalkylenes, polyhaloalkylenes, poly (alkylene phthalate or terephthalate), poly (pheny or phenylene), poly (phenylene oxide or sulfide), polyvinyl acetates, alcohols

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polyvinyls, polyvinyl halides, polyvinylidene halides, polyvinyl nitriles, polyamides, polyimides, polycarbonates, polysiloxanes, polymers of acrylic or methacrylic acid, polyacrylates or methacrylates, natural polymers such as cellulose and its derivatives, synthetic polymers such as synthetic elastomers, or thermoplastic copolymers comprising at least one monomer identical to any of the monomers included in the above-mentioned polymers, as well as mixtures and / or alloys of all these (co) polymers.

To clarify things, we can indicate that the matrix can consist of at least one of the following polymers or copolymers: Polyacrylamide, polyacrylonitrile, poly (acrylic acid), ethylene-acrylic acid copolymers, ethylene copolymers vinyl alcohol, methyl methacrylate-styrene copolymers, ethylene-ethyl acrylate copolymers, (meth) acrylate-butadiene-styrene (ABS) copolymers, and polymers of the same family; polyolefins such as low density poly (ethylene), poly (propylene), low density chlorinated poly (ethylene), poly (4-methyl-1-pentene), poly (ethylene), poly (styrene), and polymers of the same family; ionomers: poly (epichlorohydrin); poly (urethane) such as polymerization products of diols such as glycerin, trimethylol-propane, 1,2, 6-hexanetriol, sorbitol, pentaerythritol, polyether polyols, polyester polyols and compounds of the same family with polyisocyanates such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, 4,4'-dicycohexylmethane diisocyanate and compounds of the same family; and polysulfones such as the reaction products between a sodium salt of 2,2-bis (4-hydroxyphenyl) propane and 4,4'ichlorodipheryl sulfone; furan resins such as poly (furan); cellulose-ester plastics such as cellulose acetate, cellulose acetatebutyrate, cellulose propionate and polymers of the same family; silicones such as poly (dimethyl siloxane), poly (dimethyl siloxane co-phenylmethyl siloxane), and polymers of the same family; mixtures of at least two of the above polymers.

Advantageously, the thermoplastic polymer matrix M is made of polyester, such as polyethylene terephthalate (PET), polypropylene terephthalate (PPT), polybutylene terephthalate (PBT), their copolymers and mixtures.

Even more preferably, the thermoplastic polymer (s) is selected from the group of (co) polyamides comprising: Nylon 6, Nylon 6.6,

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Nylon 4, Nylon 11, Nylon 12, polyamides 4-6,6-10, 6-12,6-36, 12-12, their copolymers and blends.

As other preferred polymers of the invention, mention may be made of semi-crystalline or amorphous polyamides, such as aliphatic polyamides, semiaromatic polyamides and more generally, linear polyamides obtained by polycondensation between a saturated aliphatic or aromatic diacid, and an aromatic saturated primary diamine. or aliphatic, polyamides obtained by condensation of a lactam, of an amino acid or linear polyamides obtained by condensation of a mixture of these different monomers.

More precisely, these copolyamides can be, for example, hexamethylene polyadipamide, polyphthalamides obtained from terephthalic and / or isophthalic acid such as the polyamide marketed under the trade name AMODEL, copolyamides obtained from adipic acid , hexamethylene diamine and caprolactam.

In accordance with a preferred embodiment of the invention, the thermoplastic (co) polymer (s) is (are) a polyamide 6.6.

According to a particular embodiment of the invention, the thermoplastic polymer (s) is a polyamide 6, the relative viscosity of which, measured at 25 ° C. at a concentration of 0.01 g / ml in a 96% sulfuric acid solution is greater than 3.5, preferably greater than 3.8.

According to another advantageous characteristic of the invention, the polymer matrix (M) of the composition consists of a mixture and / or alloy of a polyamide with one or more other polymers, preferably polyamides or copolyamides.

A mixture and / or alloy of (co) polyamide with at least one polymer of the polypropylene oxide (PPO), polyvinyl chloride (PVC), polyacrylobutadiene-styrene (ABS) type is also possible.

To improve the mechanical properties of the composition according to the invention, it may be advantageous to add to it at least one reinforcing and / or filling filler chosen from the group comprising fibrous fillers such as glass fibers, aramid fibers, ceramic or carbon, mineral fillers such as clays, kaolin, or reinforcing nanoparticles or thermosetting material, and powder fillers such as talc.

The rate of incorporation into reinforcing filler complies with standards in the field of composite materials. It may for example be a loading rate of 1 to 90%, preferably 10 to 60%, and more specifically 50%.

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The PAHB additives can also be combined with other reinforcing additives such as impact modifiers such as optionally grafted elastomers.

autres additifs ou adjuvants appropriés, par exemple des charges de remplissage (Si02), des ignifugeants, des stabilisants aux UV, à la chaleur, des matifiants (Ti02), des lubrifiants, des plastifiants, des composés utiles pour la catalyse de la synthèse de la matrice polymère, des antioxydants, des antistatiques, des pigments, des colorants, des additifs d'aide au moulage ou des tensioactifs. Cette liste n'a aucun caractère limitatif. Naturally, the composition according to the invention can also contain all

other suitable additives or adjuvants, for example fillers (Si02), flame retardants, UV stabilizers, heat stabilizers, mattifiers (Ti02), lubricants, plasticizers, compounds useful for the catalysis of the synthesis of the polymer matrix, antioxidants, antistats, pigments, colorants, molding aid additives or surfactants. This list is not exhaustive.

The compositions according to the invention can be used as raw material in the field of technical plastics, for example for the production of articles molded by injection or by injection / blow molding, extruded by conventional extrusion or by extrusion blow molding, or of films.

The compositions according to the invention can also be put in the form of yarns, fibers or filaments by melt spinning.

The functionalized PAHB additive of the invention is introduced into the thermoplastic polymer matrix, preferably polyamide.

To do this, one can have recourse to any known methods of introducing particles into a matrix.

A first method could consist in mixing the functionalized PAHB in the molten matrix, and optionally in subjecting the mixture to high shearing, for example in a twin-screw extrusion device, in order to achieve good dispersion. Such a device is generally placed upstream of the means for shaping the molten plastic material (molding, extrusion, extrusion). According to a usual embodiment, this mixture is extruded in the form of rods which are then cut into granules. The molded parts are then made by melting the granules produced above and feeding the composition in the molten state into suitable molding, injection, extrusion or spinning devices.

In the case of the manufacture of yarns, fibers and filaments, the composition obtained at the extruder outlet optionally directly supplies a spinning installation.

A second method may be that which consists in mixing the PAHB with the monomers, in the polymerization medium of the thermoplastic matrix or during the polymerization.

According to a variant, one could mix with the molten matrix, a concentrated mixture of a resin and functionalized PAHB, prepared for example according to one of the methods described above.

According to another of its aspects, the present invention relates to articles obtained by shaping, preferably by molding, injection molding, injection / blow molding,

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extrusion, extrusion / blow molding or spinning, of one of the polymer compositions containing PAHB and as defined above.

These articles can be yarns, fibers, films, or filaments.

They may also be articles molded from the composition according to the invention comprising polyamide, PAHB as defined above, and optionally reinforcing fibers (glass).

A subject of the invention is also the use, as agent for modifying the rheological behavior of a thermoplastic polymer matrix, of functionalized hyperbranched copolyamide as defined above.

Other details and advantages of the invention will emerge more clearly in view of the examples given below, purely by way of illustration.

EXAMPLES Examples 1 to 5: Synthesis of PAHB based on BTC / AIP A / CL! C 16 or C 18 alkyl (example 5) Example 6: Characterization of the PAHBs of examples 1 to 4.

Example 7 Preparation of compositions according to the invention based on polyamide PA 6.6, on glass fibers, and on alkylated PAHBs according to Examples 1 to 3, at various incorporation rates.

Example 8 Preparation of composition according to the invention without glass fibers based on PA 6.6, PAHB of Examples 1 and 2 according to two incorporation rates.

Example 9: Evaluation of the rheological and mechanical characteristics of the compositions of Examples 7 and 8.

Example 10 Measurement of the values of the pack pressure decreases (die head) during the spinning of the functionalized M / PAHB compositions of Examples 2 and 4
Description of Figures:
The attached FIG. 1 is a histogram of the variation in the gain in spiral length for the PA6 compositions. 6 + 50% glass fibers + PAHB / C 16 of Table II.

Figure 2 gives a histogram of spiral length gains for the PA6.6 + PAHB / C16 compositions of Table III.

FIG. 3 accounts for the fluidity / impact resistance compromise by giving the impact resistance as a function of the spiral length for the compositions of Table II. The legend for Figure 3 is as follows:

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. : witness PA6. 6 + 50% FV; D: PA6.6 + 50% FV + 2% PAHB / CI6 ex. 1; #: PA6.6 + 50% FV + 5% PAHB / C16 ex. 1; 0: PA6. 6 + 50% FV + 2% PAHB / CI6 eX. 2; PA6. 6 + 50% FV + 5% PAHB / CI6 ex. 2; A: PA6. 6 + 50% FV + 2% PAHB / CI6 eX. 3; : PA6.6 + 50% + 5% PAHB / Cl6 eX. 3 Example 1: Synthesis of a hyperbranched copolyamide with hexadecylamide endings by melt-phase copolycondensation of 1,3,5-benzene tricarboxylic acid (noted BTC, cour molecule of R-B3 type, with B = COOH), of l '5-aminoisophthalic acid (denoted AIPA, branching molecule type A-R'-B2, with A = NH2), # - caprolactam (denoted CL, spacer type AR "-B) and nhexadecylamine ( denoted C16, alkyl blocker type R "'- A). The respective overall composition is 1/25/25/28 in BTC / AIPA / CL / C16, (III / I + II + IV = 1/78)
The reaction is carried out at atmospheric pressure in an autoclave of 7.5! commonly used for the melt synthesis of polyesters or polyamides.

The monomers are fully charged at the start of the test in the reactor preheated to 70 ° C. and with stirring at 80 rpm. 1685.0 g of molten hexadecylamine at 90% purity (6.28 mol), 634.6 g of scaprolactam (5.61 mol), 1015.8 g of 5-aminoisophthalic acid are successively introduced into the reactor. (5.61 mol), 47.1 g of 1,3,5-benzene tricarboxylic acid (0.22 mol) and 6.0 g of a 50% (w / w) aqueous solution of hypophosphorous acid . The reactor is purged by a succession of 4 sequences of placing under vacuum and restoring atmospheric pressure using dry nitrogen.

After 30 minutes under stirring at 260 ° C., the reactor is placed under progressive vacuum over 60 min. The minimum vacuum is then maintained for an additional 30 min. 229.5 g of distillate are recovered.

At the end of the cycle, the stirring is stopped and the reactor is placed under nitrogen overpressure. Then, the bottom valve is gradually opened and the polymer is poured at 260 ° C. into a stainless steel bucket. The product is then cooled in dry ice under a stream of nitrogen. 2900g of polymer are collected.

The hyperbranched copolyamide obtained is glassy and can easily be crushed into flakes or ground.

<Desc / Clms Page number 16>

Example 2: Synthesis of a hyperbranched copolyamide with hexadecylamide endings by melt-phase copolycondensation of 1,3,5-benzene tri-carboxylic acid (denoted BTC, court molecule of R-B3 type, with B = COOH), of l '5-aminoisophthalic acid (denoted AIPA, branching molecule type A-R'-B2, with A = NH2), le-caprolactam (denoted CL, spacer type AR "-B) and nhexadecylamine (denoted C16 , alkyl blocker type R "'- A). The respective overall composition is 1/6/6/9 in BTC / AIPA / CL / C16, (III / 1 + II + IV = 1/21)
The assembly and the operating mode used are strictly identical to those described in Example 1.

Are successively charged into the reactor preheated to 70 ° C.: 1867.4 g of molten hexadecylamine at 90% purity (6.96 mol), 525.1 g of s-caprolactam (4.64 mol), 840.6 g of '5-aminoisophthalic acid (4.64 mol), 162.5 g of 1,3,5-benzene tricarboxylic acid (0.77 mol) and 6.1 g of a 50% aqueous solution (w / w ) hypophosphorous acid.

After 30 minutes under stirring at 260 ° C., the reactor is placed under vacuum to complete the polycondensation. 155.2 g of distillate are collected.

At the end of the cycle, the polymer is expelled through the bottom valve at 260 ° C. in a stainless steel beaker, then cooled in dry ice under a stream of nitrogen. 2946g of polymer are collected.

The hyperbranched copolyamide obtained is glassy.

Example 3: Synthesis of a hyperbranched copolyamide with hexadecylamide endings by melt-phase copolycondensation of 1,3,5-benzene tricarboxylic acid (denoted BTC, core molecule of R-B3 type, with B = COOH), of 5-aminoisophthalic acid (denoted AIPA, branching molecule of type A-R'-B2, with A = NH2), s-caprolactam (denoted CL, spacer of type AR "-B) and nhexadecylamine (denoted C16, R "'- A type alkyl blocker). The respective overall composition is 1/20/40/23 in BTC / AIPA / CL / C16, (III / 1 + II + IV = 1/83)
The assembly and the operating mode used are strictly identical to those described in Example 1.

Are successively loaded into the reactor preheated to 70 C: 1408.9 g of hexadecylamine melted at 90% purity (5.25 mol), 1033.5 g of E-caprolactam (9.13 mol), 827.2 g of 5-aminoisophthalic acid (4.57 mol), 48.0 g of 1,3,5-benzene tricarboxylic acid (0.23 mol) and 6.5 g of a 50% aqueous solution (p / p) hypophosphorous acid.

The reactor is stirred and heated as in Example 1.193, 4 g of distillate are collected.

<Desc / Clms Page number 17>

At the end of the cycle, the polymer is poured into a stainless steel beaker, then cooled in dry ice under a stream of nitrogen. 2837.5 g of polymer are collected.

The hyperbranched copolyamide obtained is glassy.

Example 4: Synthesis of a hyperbranched copolyamide with hexadecylamide endings by melt-phase copolycondensation of 1,3,5-benzene tricarboxylic acid (noted BTC, core molecule of R-B3 type, with B = COOH), of 5-aminoisophthalic acid (denoted AIPA, branching molecule of type A-R'-B2, with A = NH2), e-caprolactam (denoted CL, spacer of type AR "-B) and nhexadecylamine (denoted C16, R "'- A type alkyl blocker). The respective overall composition is 1/5/10/8 in BTC / AIPA / CL / C16, (III / 1 + II + IV = 1/23)
The reaction is carried out at atmospheric pressure in a 1.0 L autoclave commonly used in the laboratory for the melt synthesis of polyesters or polyamides.

The monomers are fully loaded at the start of the test into the reactor at 20 ° C. 190.4 g of solid hexadecylamine at 90% purity (0.71 mol), 100.4 g of s-caprolactam are successively introduced into the reactor. (0.89 mol), 80.4 g of 5aminoisophthalic acid (0.44 mol), 18.6 g of 1,3,5-benzene tricarboxylic acid (0.09 mol) and 0.76 g of a 50% (w / w) aqueous solution of hypophosphorous acid.

After 63 minutes under stirring at 260 ° C., the reactor is placed under progressive vacuum over 61 min. The minimum vacuum achieved is 1 to 2 mBar and is then maintained for an additional 30 min. About 8 ml of distillate are collected.

At the end of the cycle, the stirring is stopped and the reactor is placed under nitrogen overpressure. The bottom valve is gradually opened and the polymer is poured into a stainless steel beaker. The product is then cooled in dry ice under a stream of nitrogen.

339 g of polymer are collected, including the samples during the synthesis.

The hyperbranched copolyamide obtained is glassy.

Example 5: Synthesis of a hyperbranched copolyamide with Octadecylamide terminations by melt-phase copolycondensation of 1,3,5-benzene tricarboxylic acid (denoted BTC, core molecule of R-B3 type, with B = COOH), of 5-aminoisophthalic acid (denoted AIPA, branching molecule of type A-R'-B2, with A = NH2), e-caprolactam (denoted CL, spacer of type AR "-B) and nOctadecylamine (denoted C18, R "'- A type alkyl blocker). The respective overall composition is 1/6/6/9 in BTC / AIPA / CL / C18, (III / 1 + Il + IV = 1/21)

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La réaction est effectuée à pression atmosphérique dans un autoclave en verre de 0, 5 1 utilisé couramment en laboratoire pour la synthèse en phase fondue de polyesters ou de polyamides.

The reaction is carried out at atmospheric pressure in a 0.5 liter glass autoclave commonly used in the laboratory for the melt synthesis of polyesters or polyamides.

Are successively loaded into the reactor at 90 C: 122.0 g of Octadecylamine in pellets at 90% purity (0.41 mol), 30.9 g of s-caprolactam (0.27 mol), 49.4 g of '5-aminoisophthalic acid (0.27 mol), 9.6 g of 1, 3, 5-benzene tricarboxylic acid (0.05 mol) and 0.25 g of a 50% (w / w) aqueous solution ) hypophosphorous acid.

The temperature is maintained at 260 ° C. with stirring for 60 minutes. The reactor is then placed under progressive vacuum over 38 min. The minimum vacuum achieved is 5 mBar and is then maintained for an additional 65 min. 12. 5 g of distillate are collected.

At the end of the cycle, the polymer is cooled in the reactor under a stream of nitrogen.

157.9 g of polymer are collected (without taking into account the samples in progress). Hyperbranched copolyamide is glassy and can easily be crushed into flakes or crushed.

Example 6: Characterization of hyperbranched polyamides with alkyl terminations with different ratios A-R'-B2 / AR "-B and different molar masses Different hyperbranched polymers are synthesized according to the protocols described in Examples 1 to 4. In all cases, the AR "-B monomer is s-caprolactam and that A-R'-B2 is 5-amino isophthalic acid.

The contents of terminal acid and amine groups are determined by potentiometry. The molar masses are determined by gel permeation chromatography (GPC) in DiMethyl Acetamide, relative to polystyrene standards, then by detection by IR refractometry.

The results are collated in Table I below.

<Desc / Clms Page number 19>

TABLE 1

<tb>
<tb>? <SEP> Composition <SEP> Ratio <SEP> Mn <SEP> GTA <SEP> GTC <SEP> Mn <SEP> Mw <SEP> Mz <SEP> IP
<tb> theoretical
<tb> BTC / AIPA / AR'B <SEP> (g / mo1) <SEP> (meq / Kg) <SEP> (meq / Kg) <SEP> (g / mol) <SEP> (g / mol) <SEP> (g / mol)
<tb> CL / C <SEP> 16 <SEP> 2 /
<tb> AR "B
<tb> 1 <SEP> 1/25/25/28 <SEP> 1/1 <SEP> 13375 <SEP> 2, <SEP> 4 <SEP> 20.4 <SEP> 6020 <SEP> 11240 <SEP> 17830 <SEP> 1, <SEP> 87
<tb> 0.6 <SEP> 1, <SEP> 6
<tb> 2 <SEP> 1/6/6/9 <SEP> 1/1 <SEP> 3879 <SEP> 3, <SEP> 1 <SEP> 7, <SEP> 7 <SEP> 4890 <SEP> 7750 <SEP> 11440 <SEP> 1, <SEP> 58
<tb> 0, <SEP> 3 <SEP> 1.8
<tb> 3 <SEP> 1/20/40/23 <SEP> 1/2 <SEP> 13139 <SEP> 3, <SEP> 7 <SEP> 35, <SEP> 7 <SEP> 6780 <SEP> 13250 <SEP> 21600 <SEP> 1, <SEP> 95
<tb> 0, <SEP> 4 <SEP> 1, <SEP> 2
<tb> 4 <SEP> 1/5/10/8 <SEP> 1/2 <SEP> 3945 <SEP> 14, <SEP> 0 <SEP> 15, <SEP> 5 <SEP> 4860 <SEP> 7630 <SEP> 11280 <SEP> 1.57
<tb> 0.5 <SEP> 0.7
<tb>
Abbreviations:

<tb>
<tb> - <SEP> BTC <SEP>: <SEP><SEP> benzene <SEP> tricarboxylic acid <SEP> or <SEP> trimesic
<tb> - <SEP> AIPA <SEP>: <SEP> 5-Amino <SEP> Isophthalic Acid <SEP>
<tb> - <SEP> CL <SEP>: <SEP> s-caprolactam
<tb> - <SEP> C16 <SEP>: <SEP> n-Hexadecylamine
<tb> - <SEP> GTA <SEP>: <SEP> Content <SEP> in <SEP> groups <SEP> terminals <SEP> amine
<tb> - <SEP> GTC <SEP>: <SEP> Content <SEP> in <SEP> groups <SEP> terminals <SEP> acid
<tb> - <SEP> Mn, <SEP> Mw, <SEP> Mz <SEP>: <SEP> molar <SEP> masses <SEP> average <SEP> in <SEP> equivalent <SEP> polystyrene
<tb> - <SEP> IP <SEP>: <SEP> index <SEP> of <SEP> polymolecularity
<tb>

The DSC analyzes of these hyperbranched polyamides only show a broad melting peak around −4 C. This peak corresponds to the alkyl segments and underlines the phase micro segregation of the hydrophobic units with respect to the polyamide ones.

Example 7: preparation of mixtures of polyamide matrix PA 6. 6 / glass fibers / additive modifying the rheological behavior PAHB alkylated C16
The PAHBs of Examples 1, 2 and 3 are coarsely ground and premixed in the desired proportions with granules of PA 6.6.

PA 6.6 is defined as follows: viscosity index measured at 25 C in 90% formic acid (ISO 307) of 137, content of amine end groups of 53 meq / kg and content of acid end groups of 72 meq / kg.

<Desc / Clms Page number 20>

Compositions containing 50% by weight of glass fibers (Owens Coming OCF180K) and a PA 6.6 matrix supplemented with variable amounts of the PAHBs of Examples 1, 2 and 3 are produced by mixing in the molten state at a temperature of 280 C. in a twin-screw extruder.

A control is also prepared consisting of a thermoplastic composition based on PA 6.6 and 50% by weight of glass fibers.

The rheological and mechanical properties of these compositions are evaluated in Example 9.

Example 8: preparation of mixtures of PA 6.6 + C16 alkylated PAHB matrix
The PA 6.6 used is the same as in Example 7 and the C16 alkylated PAHBs are those of Examples 2 and 1, at rates of 5 and 10% (only 10% for Example 1) by weight relative to total of the mixture.

The rheological and mechanical evaluations are given in Example 9 below.

Example 9: rheological and mechanical evaluation of the compositions of Examples 7 and 8
The tests used are: - TS spiral test (fluidity in the molten state) for quantifying the fluidity of the compositions according to the invention and of the control compositions:
The granules of composition M / PAHB or of control composition M are melted and then injected into a spiral-shaped mold with a semi-circular section 2 mm thick and 4 mm in diameter, in a DEMAG H200-80 press at a temperature of sleeve of 300 C, a mold temperature of 80 C and with an injection pressure of 1500 bars. The injection time is 0.5 seconds. The result is expressed as the length of the mold correctly filled by the composition. The compositions evaluated in this test all have a moisture content before molding equivalent to within 0.1% relative to the matrix.

- Mechanical tests: The mechanical characteristics are evaluated by impact tests without notch (ISO 179 / leU), impact with notch (ISO 179 / leA), flexural modulus ISO 178, flexural stress at break ISO 178 and bending temperature under load (HDT) ISO 75Ae.

The results are given in Tables II and III below.

<Desc / Clms Page number 21>

TABLE II Compositions filled with 50% glass fibers (FV)

<tb>
<tb> Composition <SEP> Length <SEP> Rate <SEP> Mass <SEP> of <SEP>% <SEP> of <SEP> the <SEP> Shock <SEP> without <SEP> Shock <SEP> with <SEP > Module <SEP> in <SEP> Constraint <SEP> HDT <SEP> (C)
<tb> spiral <SEP> of humidity <SEP> PA <SEP> variation <SEP> of <SEP> the <SEP> notch <SEP> notch <SEP> bending <SEP> rupture <SEP> (1.80
<tb> (mm) <SEP> before <SEP> (g / mol) <SEP> ** <SEP> mass <SEP> by <SEP> (KJ / m2) <SEP> (KJ / m2) <SEP> (N / mm2) <SEP> in <SEP> bending <SEP> N / mm2)
<tb> molding <SEP> ratio <SEP> to <SEP> the <SEP> ISO <SEP> ISO <SEP> ISO <SEP> 178 <SEP> (N / mm2) <SEP> ISO <SEP> 75Ae
<tb> (%) <SEP> * <SEP> mass <SEP> of <SEP> 179/1 <SEP> Eu <SEP> 179/1 <SEP> eA <SEP> ISO <SEP> 178
<tb> witness
<tb> WITNESS
<tb> PA66 / 50% FV <SEP> 339 <SEP> 0.20 <SEP> 65250 <SEP> 82, <SEP> 4 <SEP> 11.0 <SEP> 11800 <SEP> 280 <SEP> 248
<tb> PA66 / 50% <SEP> FV <SEP> 363 <SEP> 0.18 <SEP> 62440-4, <SEP> 3 <SEP> 76.2 <SEP> 10.5 <SEP> 11500 <SEP > 268 <SEP> 245
<tb> + <SEP> 2% <SEP> PAHB / C16
<tb> ex. <SEP> 1
<tb> PA66 / 50% <SEP> FV <SEP> 383 <SEP> 0.18 <SEP> 69830 <SEP> +7, <SEP> 0 <SEP> 71.6 <SEP> 10.4 <SEP> 12100 <SEP> 270 <SEP> 248
<tb> + <SEP> 5% <SEP> PAHB / C16
<tb> ex. <SEP> 1
<tb> PA66 / 50% <SEP> FV <SEP> 430 <SEP> 0.26 <SEP> 63550-2, <SEP> 6 <SEP> 76.3 <SEP> 10.3 <SEP> 11500 <SEP > 262 <SEP> 245
<tb> + <SEP> 2% <SEP> PAHB / C16
<tb> ex. <SEP> 2
<tb> PA66 / 50% <SEP> FV <SEP> 512 <SEP> 0.20 <SEP> 63420-2, <SEP> 8 <SEP> 75.9 <SEP> 10, <SEP> 0 <SEP> 10900 <SEP> 256 <SEP> 245
<tb> + <SEP> 5% <SEP> PAHB / C16
<tb> ex. <SEP> 2
<tb> PA66 / 50% <SEP> FV <SEP> 399 <SEP> 0.24 <SEP> 62530-4, <SEP> 2 <SEP> 74.5 <SEP> 10.2 <SEP> 11500 <SEP > 261 <SEP> 245
<tb> + <SEP> 2% <SEP> PAHB / C16
<tb> ex. <SEP> 3
<tb> PA66 / 50% <SEP> FV <SEP> 440 <SEP> 0.18 <SEP> 64970-0, <SEP> 4 <SEP> 67.9 <SEP> 10.1 <SEP> 11700 <SEP > 262 <SEP> 245
<tb> + <SEP> 5% <SEP> PAHB / C16
<tb> ex. <SEP> 3
<tb>

<Desc / Clms Page number 22>

* Moisture content with respect to the matrix measured by the Karl-Fischer method ** Maximum of the molecular weight distribution of the polyamide matrix with the addition of functionalized PAHB, in polystyrene equivalent, measured by Gel Permeation Chromatography (GPC) in refractometric detection after implementation of the spiral fluidity quantification test.

TABLE III (example 8)
Compositions without glass fibers

<tb>
<tb> Composition <SEP> Length
<tb> spiral <SEP> (mm)
<tb> PA66 <SEP> 556
<tb> PA66 <SEP> + <SEP> 5% <SEP> 588
<tb> PAHB / CI6 <SEP> eX. <SEP> 2
<tb> PA66 <SEP> + <SEP> 10% <SEP> 988
<tb> PAHB / C16 <SEP> eX. <SEP> 2
<tb> PA66 <SEP> + <SEP> 10% <SEP> 866
<tb> PAHB / Cex. <SEP> l
<tb>
Example 10 Measurement of the values of the pack pressure decreases (die head) during the spinning of the functionalized M / PAHB compositions of Examples 2 and 4 The polyamide 66 used is a Polyamide 66 not comprising titanium dioxide, of relative viscosity of 2.5 (measured at a concentration of 10 g / l in 96% sulfuric acid).

. The incorporation of the PAHB (2 or 5% by weight relative to the total weight of the composition) in the PA66 is carried out by mixing powders then in the molten phase using a twin-screw extrusion device. The molten mixture is then spun with a speed at the first pick-up point of 800 m / min, so as to obtain a continuous multifilament yarn of 90 dtex for 10 filaments.

The temperature-pressure and spinning rate as well as the properties of the yarns obtained are specified below: 0 Spinning rate: no breakage 0 Twin-screw extruder heating: 285 C 0 Screw rotation speed: 120 rpm 0 Head heating line: 287 C 0 Flow rate under the line: 0.41 kg / h.

The multifilament or yarn consists of 10 strands (the die consists of 10 holes) and the diameter of one strand is about 30 µm.

<Desc / Clms Page number 23>

The values of the pack pressure decreases (die head) are measured using a Dynisco probe pressure (0-350 bar).

The results obtained are given in Table IV below.

TABLE IV

<tb>
<tb> Composition <SEP> Pressure <SEP> of <SEP> pack <SEP> Delta <SEP> Mass <SEP> of <SEP> PA <SEP> by
<tb> (bars) <SEP> pressure / indicator <SEP> GPC <SEP> with <SEP> detection
<tb> to <SEP> refractometer <SEP> *
<tb> PA <SEP> 66 <SEP> indicator <SEP> 35.4 <SEP> 66 <SEP> 000
<tb> PA <SEP> 66 <SEP> + <SEP> 5% <SEP> 1/5/10/8 <SEP> 25, <SEP> 5-28, <SEP> 0% <SEP> 67000
<tb> example <SEP> 4
<tb> PA <SEP> 66 <SEP> + <SEP> 5% <SEP> 1/6/6/9 <SEP> 28, <SEP> 0-20, <SEP> 9 <SEP>% <SEP> 66 <SEP> 000
<tb> example <SEP> 2
<tb> PA <SEP> 66 <SEP> + <SEP> 2% <SEP> 1/5/10/8 <SEP> 33, <SEP> 0-6, <SEP> 8 <SEP>% <SEP> 66 <SEP> 000
<tb> example <SEP> 4
<tb> PA <SEP> 66 <SEP> + <SEP> 2% <SEP> 1/6/6/9 <SEP> 34, <SEP> 5-2, <SEP> 5 <SEP>% <SEP> 66 <SEP> 000
<tb> example <SEP> 2
<tb>
* maximum of the molecular weight distribution of the polyamide matrix with the addition of functionalized PAHB, in polystyrene equivalent, measured by GPC in refractometric detection, after spinning.

Example H: Comparison of the molar mass of the matrices of compositions according to the invention (PA 66 / C16 alkylated PAHB / glass fibers) of the type of those of example 7 and of compositions comprising polyamide 6, an additive of the PAHB type non-functionalized and glass fibers.

11. 1-Preparation of non-functionalized PAHB: Synthesis of a hyperbranched copolyamide with carboxylic acid terminations by molten phase copolycondensation of 1,3,5-benzene tricarboxylic acid (core molecule of R'-B "3 type, with B "= COOH), 5-aminoisophthalic acid (AR-B2 type branching molecule, with A = NH2 and B = COOH) and ls-caprolactam (A'-R'-B 'type spacer with A '= NH2 and B' = COOH).

The reaction is carried out at atmospheric pressure in a 7.5 l autoclave commonly used for the melt-phase synthesis of polyesters or polyamides.

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The monomers are fully charged at the start of the test. 1811.5 g of 5-aminoisophthalic acid (10 mol), 84 g of 1,3,5-benzene tricarboxylic acid (0.4 mol), 1131.6 g of s-caprolactam (10 mol) are successively introduced into the reactor. mol) and 1.35 g of a 50% (w / w) aqueous solution of hypophosphorous acid. The reactor is purged by a succession of 4 sequences of placing under vacuum and restoring atmospheric pressure using dry nitrogen.

The reaction mass is gradually heated from 20 to 200 C in 100 min., Then from 200 to 245 C in 60 min. When the mass temperature reaches 100 ° C., stirring is started with a rotational speed of 50 revolutions per minute. The distillation begins at a bulk temperature of 160 ° C. and continues up to a temperature of 243 ° C. At 245 ° C., the stirring is stopped and the reactor is placed under nitrogen overpressure.

Then, the bottom valve is gradually opened and the polymer is poured into a stainless steel bucket filled with water.

The water contained in the 221.06 g of distillate collected is titrated using a Karl Fischer coulometer. The water content of the distillate is 81.1%, which translates to an overall progress rate of 99.3%.

The hyperbranched copolyamide obtained is soluble at room temperature in the quantity of aqueous sodium hydroxide necessary to neutralize the terminal acid functions.

11. 2 — Preparation of the compositions PA 6 + non-functionalized PAHB according to 11. 1 + glass fibers and of a control composition free of non-functionalized PAHB.

The procedure is as indicated in Example 7, except for the extrusion temperature which is here 250 C.

11. 3 — Measurement of the molar mass of the matrix of the compositions according to 11.2 and of the compositions obtained in Example 7, according to protocol P The compositions and the results are given in Table V below.

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TABLE V (exemplell) Comparison between non-functionalized PAHB (COOH terminated) and functionalized PAHB (alkyl terminated) on granules mixed with PA (resulting from extrusion)

<tb>
<tb> Composition <SEP> of <SEP> granules <SEP> Mass <SEP> of <SEP> PA <SEP>% <SEP> of <SEP> variation <SEP> of
<tb> (g / mol) <SEP> according to <SEP> the <SEP> the <SEP> mass <SEP> by
<tb> protocol <SEP> P <SEP> report <SEP> to witness <SEP>
<tb> WITNESS <SEP> 73770 /
<tb> PA66 / 50% <SEP> FV
<tb> PA66 / 50% <SEP> FV <SEP> 73690-0, <SEP> 1
<tb> + <SEP> 2% <SEP> PAHB / C16 <SEP> ex. <SEP> 1
<tb> PA66 / 50% <SEP> FV <SEP> 74320 <SEP> +0, <SEP> 7
<tb> + <SEP> 5% <SEP> PAHB / CI6 <SEP> ex. <SEP> 1
<tb> PA66 / 50% <SEP> FV <SEP> 75020 <SEP> + <SEP> 1, <SEP> 7
<tb> + <SEP> 2% <SEP> PAHB / C16 <SEP> ex. <SEP> 2
<tb> PA66 / 50% <SEP> FV <SEP> 75650 <SEP> + <SEP> 2, <SEP> 4
<tb> + 5% <SEP> PAHB / Cl6ex. <SEP> 2
<tb> PA66 / 50% <SEP> FV <SEP> 74780 <SEP> +1, <SEP> 4
<tb> + <SEP> 2% <SEP> PAHB / C16 <SEP> ex. <SEP> 3
<tb> PA66 / 50% <SEP> FV <SEP> 75330 <SEP> +2, <SEP> 1
<tb> + <SEP> 5% <SEP> PAHB / CI6 <SEP> ex. <SEP> 3
<tb> WITNESS <SEP> 75000 /
<tb> PA6 / 50% <SEP> FV <SEP> according to <SEP> 11.2
<tb> PA6 / 50% <SEP> FV <SEP> 70000-6, <SEP> 6
<tb> + <SEP> 2% <SEP> PAHB / COOH <SEP> according to <SEP> 11. <SEP> 2
<tb> PA6 / 50% <SEP> FV <SEP> 60000-20
<tb> + <SEP> 5% <SEP> PAHB / COOH <SEP> according to <SEP> 11. <SEP> 2
<tb> PA6 / 50% <SEP> FV <SEP> 57000-24
<tb> + <SEP> 10% <SEP> PAHB / COOH <SEP> according to <SEP> 11. <SEP> 2
<tb>

Claims (20)

CLAIMS -1- Thermoplastic polymer composition characterized in that it comprises: # a matrix M based on at least one thermoplastic polymer, # and at least one PAHB additive modifying the rheological behavior comprising at least one copolyamide:> functionalized, # hyperbranched of the type of those obtained by reaction between: 'at least one monomer of the following formula (1): (1) AR-Bf in which A is a reactive polymerization function of a first type, B is a reactive polymerization function of a second type and capable of reacting with A, R is a hydrocarbon entity optionally comprising heteroatoms, and f is the total number of reactive functions B per monomer: f 2, preferably 2::; f::; 10; * optionally at least one bifunctional spacer monomer of the following formula (II): (II) A'-R'-B 'or the corresponding lactams, in which A', B ', R' have the same definition as that given above respectively for A, B, R in formula (I); optionally at least one "core" monomer of formula (III): (III) R1 (B ") n in which: * R1 is a substituted or unsubstituted hydrocarbon radical, of the silicone, linear or branched alkyl, aromatic, alkylaryl or arylalkyl type or cycloaliphatic which may comprise unsaturations and / or heteroatoms; * B "is a reactive function of the same nature as B or B '; * n 1, preferably 1::; not : : ; 100; <Desc / Clms Page number 27> . and at least one “chain-limiting” functionalizing monomer corresponding to formula (IV): (IV) RA ”in which: R2 is a substituted or unsubstituted hydrocarbon radical of the silicone, linear or branched alkyl, aromatic or arylalkyl type. , alkylaryl or cycloaliphatic which may comprise one or more unsaturations and / or one or more heteroatoms, and A "is a reactive function of the same nature as A or A '; at least 50% of the end groups of this hyperbranched copolyamide are functionalized with R2. - 2-Composition according to claim 1, characterized in that it is free of PAHB additives resulting in a decrease in the molar mass of the matrix M greater than or equal to 7% relative to a control composition comprising the same matrix M not additive with PAHB, the molar mass measurement being carried out according to a determined P protocol. - 3-Composition according to claim 2, characterized in that the molar mass measurement is carried out on the composition to be analyzed and on the control composition extruded, solidified and then placed in the form of granules. - 4-Composition according to claim 2, characterized in that the molar mass measurement is carried out on the composition to be analyzed and on the control composition extruded, solidified, put in the form of granules and then subjected to a determined Qf test for quantifying their fluidity. - 5-Composition according to claim 1, characterized in that, in the hyperbranched copolyamide constituting the additive PAHB: the hydrocarbon entities R, R ′ of the monomers (1) and (II) respectively, each comprise: i. at least one linear or branched aliphatic radical; ii. and / or at least one cycloaliphatic radical; iii. and / or at least one aromatic radical comprising one or more aromatic rings; iv. and / or at least one arylatiphatic radical; <Desc / Clms Page number 28> B, B ′ is a reactive function of the acid, ester, acid halide or amide type or of the amine or amine salt type. A, A ′ is a reactive function of the amine, amine salt or acid, ester, acid halide or amide type; these radicals (i), (ii), (iii), (iv) possibly being substituted and / or comprising heteroatoms; - 6-Composition according to claim 1 or 2, characterized in that the reactive polymerization functions A, B, A ', B' of the hyperbranched copolyamide are chosen from the group comprising the carboxylic and amine functions.

- 7-Composition according to any one of claims 1 to 6, characterized in that the hyperbranched copolyamide (PAHB) comprises monomers (III) in a molar ratio III / 1 + II + IV being defined as follows: - 8-Composition according to any one of claims 1 to 7, characterized in that the monomer of formula (1) of the hyperbranched copolyamide (PAHB) is a compound in which A represents the amine function, B the carboxylic function, R un aromatic radical and f = 2. <tb> <tb> and <SEP> plus <SEP> preferably <SEP> again <SEP> 111/1 <SEP> + <SEP> II <SEP> + <SEP> IV <SEP> s <SEP>: <SEP> 1 / 50. <tb> and <SEP> of <SEP> preference <SEP> III / 1 <SEP> + <SEP> II <SEP> + <SEP> IV <SEP> <<SEP> 1/100 <tb> III / I + II + IVs <SEP>: <SEP> 1/150 <tb> - 9-Composition according to any one of claims 1 to 8, characterized in that, as regards the hyperbranched copolyamide (PAHB): the monomer (1) is chosen from the group comprising: - 5-amino acid- isophthalic, - 6-amino-undecandioic acid, - 3-aminopimelic diacid, - aspartic acid, - 3,5-diaminobenzoic acid, - 3,4-diaminobenzoic acid, - and mixtures thereof; . the bifunctional monomer of formula (II) is chosen from the group comprising: - s-caprolactam and / or the corresponding amino acid: aminocaproic acid, <Desc / Clms Page number 29> - para or metaaminobenzoic acid, - 11-amino undecanoic acid, - auryllactam and / or the corresponding amino acid, - 12-amino-dodecanoic acid - and mixtures thereof; * the "core" monomer (III) is chosen from the group comprising: - 1, 3, 5-benzene tri-carboxylic acid, - 2,2, 6, 6-tetra- (ss-carboxyethyl) cyclohexanone, - 2,4,6-tri- (aminocaproic acid) -1, 3,5-triazine, - 4-aminoethyl-1, 8-octanediamine, - and mixtures thereof; * the “chain-limiting” functionalization monomer (IV) is chosen from the group comprising: - n-hexadecylamine, - n-octadecylamine - n-dodecylamine, - benzylamine, - and mixtures thereof.

- 10-Composition according to any one of claims 1 to 9, characterized in that the thermoplastic (co) polymer (s) constituting the matrix is (are) chosen from the group comprising: polyolefins, polyesters, polyalkylene oxides, polyoxyalkylenes, polyhaloalkylenes, poly (alkylene phthalate or terephthalate), poly (pheny or phenylene), poly (phenylene oxide or sulfide), polyvinyl acetates, polyvinyl alcohols, polyvinyl halides, polyvinylidene halides, polyvinyl nitriles, polyamides, polyimides, polycarbonates, polysiloxanes, polymers of acrylic or methacrylic acid, polyacrylates or methacrylates, natural polymers cellulose and its derivatives , synthetic polymers such as synthetic elastomers, or thermoplastic copolymers comprising at least one monomer identical to any of the monomers included in the polymers mentioned above, as well as mixtures and / or alloys of all these (co) polymers. - 11-Composition according to claim 10, characterized in that the thermoplastic polymer (s) is selected from the group of (co) polyamides comprising: Nylon 6, Nylon 6.6, Nylon 4, Nylon 11, Nylon 12, polyamides 4-6,6-10, 6-12,6-36, 12-12, their copolymers and mixtures. <Desc / Clms Page number 30> - 12-Composition according to claim 11, characterized in that the thermoplastic polymer (s) is a polyamide 6, the relative viscosity of which, measured at 25 C at a concentration of 0.01 g / ml in a 96% sulfuric acid solution is greater than 3.5, preferably greater than 3.8. 13. Composition according to claim 12, characterized in that the thermoplastic polymer (s) is a polyamide 6.6.

- 14-Composition according to any one of claims 1 to 13, characterized in that the additive comprising the hyperbranched copolymer is present in an amount of (expressed in% by dry weight relative to the total mass of the composition): <tb> <tb> and <SEP> plus <SEP> preferably <SEP> again <SEP> 2 <SEP> to <SEP> 10. <tb> from <SEP> preference <SEP> 1 <SEP> to <SEP> 20 <tb> 0.1 <SEP> to <SEP> 50 <tb> - 15-Composition according to any one of claims 1 to 14, characterized in that the additive comprising the hyperbranched copolymer has a content of acid or amine end groups (GT) (expressed in meq / kg) of between 0 and 25 . 16-Composition according to any one of claims 1 to 14, characterized in that it comprises at least one reinforcing and / or filling filler chosen from the group comprising fibrous fillers such as glass fibers, aramid, ceramic or carbon, mineral or thermosetting fillers, and powder fillers such as talc. - 17-Articles obtained by shaping, preferably by molding, injection molding, injection / blow molding, extrusion / blow molding, extrusion or spinning, of the composition according to any one of claims 1 to 16. - 18-Articles according to claim 17, characterized in that they are obtained by molding the composition according to any one of claims 1 to 16. - 19-Articles according to claim 17, characterized in that they are son, fibers, films or filaments. <Desc / Clms Page number 31> - 20-Use, as agent for modifying the rheological behavior of a thermoplastic polymer matrix M, of functionalized hyperbranched copolyamide as defined in the preceding claims.