EP2294113A2

EP2294113A2 - Process for preparing a polyamideimide, a polyamideimide and composition comprising this polyamideimide

Info

Publication number: EP2294113A2
Application number: EP09765750A
Authority: EP
Inventors: Franck Touraud; Véronique Bossennec; Stéphane JEOL
Original assignee: Rhodia Operations SAS
Current assignee: Rhodia Operations SAS
Priority date: 2008-06-12
Filing date: 2009-06-05
Publication date: 2011-03-16
Also published as: WO2009153170A3; FR2932486A1; KR20110013472A; WO2009153170A2; KR101308319B1; CN102099398A; CN102099398B; US20110160407A1; FR2932486B1; BRPI0909912A2

Abstract

The present invention relates to a process for preparing a semi-aromatic polyamideimide, and also to a polyamideimide and to a composition based on a thermoplastic matrix, comprising a polyamideimide. The invention relates more particularly to a process for preparing a polyamideimide by melt polymerization of at least one organic compound having carboxyl groups, of at least one diamine compound and optionally at least one diacid compound.

Description

PROCESS FOR THE PREPARATION OF A POLYAMIDEIMIDE, POLYAMIDEIMIDE AND COMPOSITION COMPRISING SAID POLYAMIDEIMIDE

The present invention relates to a process for preparing a semi-aromatic polyamideimide, and a polyamideimide and a composition based on a thermoplastic matrix, comprising a polyamideimide. The invention relates more particularly to a process for the preparation of polyamideimide by melt polymerization of at least one organic compound having carboxyl groups, at least one diamine compound and optionally at least one diacid compound.

[0002] Polyamidesimides are polymers of significant industrial and commercial interest. They are used in particular in the field of fire resistant textiles, or injected parts with high thermal resistance. Among them, semi-aromatic polyamidesimides are particularly interesting in terms of properties. Indeed they have intermediate properties between aromatic polyamidesimides on the one hand, and for example aliphatic polyamides on the other hand. Aromatic polyamidesimides are high performance polymers with very good mechanical properties. But they are difficult to synthesize and transformable in the molten route, unlike aliphatic polyamides. Semi-aromatic polyamidesimides are more easily converted than aromatic polyamidesimides (they have a glass transition temperature and a melting temperature lower than the melt forming temperatures), and they have better mechanical and thermomechanical properties than polyamides. aliphatic.

Processes for the preparation of aromatic or semi-aromatic polyamidesimides are known. These processes are generally processes for the preparation of polyamidesimide in solution in organic solvents. The use of organic solvents has major disadvantages. On the one hand, the recovery of the polymer after synthesis requires steps such as precipitation of the polymer in a non-solvent, washing and drying of the polymer. On the other hand some solvents are toxic and therefore dangerous for man and the environment.

The invention therefore provides a process for the preparation of semi-aromatic polyamideimides, which does not have these disadvantages.

Thus, the invention provides, in a first object, a process for the preparation of semi-aromatic polyamideimide by melt polymerization of at least the following monomers:

a) at least one organic compound, preferably aromatic, comprising at least two carboxyl groups, preferably at least three carboxyl groups, the carboxyl groups being present in the form of functional groups chosen from carboxylic acid, acid chloride and anhydride functions; of acid, amide or ester, at least two of the carboxyl groups forming an intramolecular anhydride function or capable of forming an intramolecular anhydride function,

b) at least one diamine compound, preferably aliphatic diamine,

c) Optionally at least one diacid compound

When all the carboxyl groups of the compound a) form an intramolecular anhydride function or can form an intramolecular anhydride function, the molar proportion of compound c) relative to the sum of the compounds a) and c) is greater than or equal to 0.5% , advantageously greater than or equal to 25%, preferably greater than or equal to 50%.

In a second subject, the invention provides a polyamideimide comprising the following recurring units:

And or

with R and R 'are aliphatic, cycloaliphatic or arylaliphatic hydrocarbon radicals, advantageously aliphatic or cycloaliphatic, preferably comprising between 2 and 18 carbon atoms

R "is a hydrocarbon radical preferably comprising between 2 and 18 carbon atoms

Y is a trivalent aromatic hydrocarbon radical

Y 'is a tetravalent aromatic hydrocarbon radical

Or a polyamideimide comprising the following recurring units:

And or

with R, R 'and R "are hydrocarbon radicals preferably comprising between 2 and 18 carbon atoms R '"is an aromatic hydrocarbon radical, preferably comprising between 2 and 18 carbon atoms

Y is a trivalent hydrocarbon radical, aromatic or aliphatic, preferably aromatic

Y 'is a tetravalent, aromatic or aliphatic hydrocarbon radical, preferably aromatic

In a third subject, the invention provides a thermoplastic polymer composition comprising the semi-aromatic polyamideimide of the invention described above or obtained by the method of the invention described above. The invention finally relates, in a fourth object, the articles obtained by shaping the composition of the invention.

The process for the preparation of polyamideimide of the invention uses as monomer at least one compound a) organic, preferably aromatic.

The compound a) has at least three functional groups selected from carboxyl groups and amino groups.

Advantageously, the compound a) comprises three or four carboxyl groups, preferably three or four carboxylic acid functions.

The compound a) may for example comprise at least one pair of carboxyl groups ortho position relative to each other.

According to a particular embodiment of the process of the invention, the compound a) is of formula (I) below:

Z- (COOH) ₃

in which Z is a trivalent aromatic radical.

Z may be a trivalent radical of benzene, naphthalene, biphenyl, diphenyl ether, diphenyl sulfide, diphenyl sulfone, ditolyl ether, and the like. [0013] Advantageously Z has between 6 and 18 carbon atoms.

This particular embodiment of the process of the invention uses carboxylic acids, which are generally less toxic than the equivalent carboxylic anhydrides.

The compound a) is preferably chosen from trimellitic acid, pyromellitic acid, their anhydrides, their esters or their amides.

Advantageously, the compound a) does not include an imide function.

The compound a) may also be a compound having an amino group and two carboxyl groups. Examples of such compounds include aspartic acid, 3-aminophthalic acid or 4-aminophthalic acid.

In the context of the invention, mixtures of different compounds a) can be implemented.

The polyamideimide preparation process of the invention uses as monomer at least one compound b) diamine.

The diamines useful in the present invention advantageously have the formula H ₂ NR-NH ₂ (II) in which R is a divalent hydrocarbon radical, in particular an aliphatic, aromatic or arylaliphatic diradical or a substituted derivative of these diradicals. The radical R advantageously comprises between 2 and 18 carbon atoms.

By arylaliphatic diamine means a diamine at least one of the amine functions is not attached to a carbon atom forming part of an aromatic ring.

Suitable aliphatic diamines include straight-chain aliphatic diamines, such as 1,10-diaminodecane, branched-chain aliphatic diamines, such as 2-methyl-1,6-diaminohexane, and cycloaliphatic diamines, such as than di (aminomethyl) cyclohexanediamines. The aliphatic chain may contain hetero atoms such as sulfur or oxygen, as represented by 3,3'-ethylenedioxybis (propylamine), and may also carry substituents, such as carbon atoms. halogen, which do not react under the polymerization conditions.

Suitable aromatic diamines in the present invention include diamines wherein R in the general formula is phenylene group, a condensed aromatic group, such as naphthylene group, or two (or more) linked aromatic rings, as shown by bisphenylene, bisphenylenemethane, bisphenylenepropane, bisphenylenesulfone, bisphenylene ether and the like. In addition, any of the aromatic groups may carry one or more substituents on the ring, such as lower alkyl groups or halogen atoms, which do not react under the polymerization conditions. The diamine preferably contains 2 to 18 carbon atoms, more preferably 4 to 12 carbon atoms. Particularly suitable diamines include diamines of the homologous series H ₂ N (CH ₂ ) InNH ₂ in which m is an integer of 2 to 12, preferably 4 to 8, and diamines of the general formula H ₂ N ( CH ₂ ) _p Z (CH ₂ ) qNH ₂ wherein Z is phenylene and p and q are independently 1, 2 or 3.

Advantageously, the compound b) is an aliphatic diamine.

The diamines may for example be chosen from hexamethylenediamine; butane diamine; 2-methyl pentamethylene diamine; 2-methyl hexamethylenediamine; 3-methyl hexamethylene diamine; 2,5-dimethyl hexamethylenediamine; 2,2-dimethylpentamethylene diamine; nonane diamine; 5-methylnonanediamine; dodecamethylene diamine; 2,2,4- and 2,4,4-trimethyl hexamethylenediamine; 2,2,7,7-tetramethyl octamethylene diamine; meta-xylylenediamine; paraxylylene diamine; isophorone diamine; diaminodicyclohexyl methane and C2-C16 aliphatic diamines which may be substituted by one or more alkyl groups. The preferred diamine is hexamethylenediamine. Mixtures of diamines can also be used in the present invention to produce polymers having recurring units wherein the group represented by R in the general formula for the polymers refers to two or more different diradicals.

Advantageously at least 45 mol%, preferably at least 50 mol% of the diamine compound is an aliphatic, cycloaliphatic or arylaliphatic diamine.

The polyamideimide preparation process of the invention also optionally performs as monomer at least one compound c) diacid.

Advantageously, the compound c) has the following formula (III):

HOOC-R'-COOH (III)

wherein R 'is a divalent aliphatic, cycloaliphatic, arylaliphatic or aromatic hydrocarbon radical.

The radical R 'preferably has between 2 and 18 carbon atoms.

By arylaliphatic diacid means a diacid which at least one of the acid functions is not attached to a carbon atom forming part of an aromatic ring.

According to a particular embodiment of the process of the invention, the compound c) is an aliphatic diacid. The aliphatic acid may for example be chosen from oxalic, maleic, succinic, pimelic and azelaic acid. It may also include unsaturations, this is the case, for example, of maleic or fumaric acid.

The dicarboxylic acids may also be chosen from glutaric acid, adipic acid, suberic acid, sebacic acid, dodecanedioic acid; 1,2-or 1,3-cyclohexane dicarboxylic acid; 1,2-or 1,3-phenylene diacetic acid; 1, 2-or 1,3-cyclohexane diacetic acid; isophthalic acid; terephthalic acid; 4,4'-benzophenone acid dicarboxylic acid; 2,5-naphthalene dicarboxylic acid; and pt-butyl isophthalic acid. The preferred dicarboxylic acid is adipic acid.

In the context of the invention, mixtures of different compounds c) can be implemented.

Advantageously, the process of the invention does not comprise lactam monomers or aliphatic amino acids, preferably no lactams or amino acids, such as caprolactam, 6-aminohexanoic acid, 5-aminopentanoic acid, the acid. 7-aminoheptanoic acid, aminoundecanoic acid, dodecanolactam.

Advantageously, the method of the invention does not comprise diol monomers. Indeed the presence of such monomers may for example result in low viscosity of the polymers obtained, which is not desirable.

The process for preparing the polyamideimide of the invention comprises a melt polymerization of the monomers a), b) and optionally c).

By the term "melt polymerization" is meant that the polymerization is carried out in the liquid state, and that the polymerization medium contains no solvent other than water, optionally. The polymerization is carried out in a continuous liquid phase. The polymerization medium may for example be an aqueous solution comprising the monomers, or a liquid comprising the monomers. Advantageously, the polymerization medium comprises water as a solvent. This facilitates the agitation of the medium, and therefore its homogeneity.

The polymerization medium may also include additives such as chain limiters.

The polyamideimide of the invention is generally obtained by polycondensation between the compound a), the compound b) and optionally the compound c) to form polyamideimide chains, with formation of the elimination product, in particular water, some of which can vaporize. The polyamideimide of the invention is generally obtained by heating at high temperature and pressure, for example an aqueous solution comprising the monomers, or a liquid comprising the monomers, to evaporate the elimination product, in particularly water (initially present in the polymerization medium and / or formed during the polycondensation) while avoiding any solid phase formation to prevent caking.

The polycondensation reaction is generally carried out at a pressure of approximately 0.5-2.5 MPa (0.5-3.5 MPa) at a temperature of approximately 215-300 ^° C. (180-320 ^° C.). VS). The polycondensation is generally continued in the melt phase at atmospheric pressure or reduced so as to reach the desired degree of advancement.

The polycondensation product is a polymer or molten prepolymer. It may comprise a vapor phase consisting essentially of vapor of the elimination product, in particular water, which may have been formed and / or vaporized.

This product can be subjected to vapor phase separation and finishing steps to achieve the desired degree of polycondensation. The separation of the vapor phase may for example be carried out in a cyclone device. Such devices are known.

The finish consists in maintaining the polycondensation product in the molten state, under a pressure close to atmospheric pressure or under reduced pressure, for a time sufficient to reach the desired degree of advancement. Such an operation is known to those skilled in the art. The temperature of the finishing step is advantageously greater than or equal to 200 ° C. and in all cases greater than the solidification temperature of the polymer. The residence time in the finishing device is preferably greater than or equal to 5 minutes.

The polycondensation product may also undergo a post-condensation phase in solid phase. This step is known to the man of and increases the degree of polycondensation to a desired value.

The process of the invention is similar in its conditions to the conventional polyamide preparation process of the type of those obtained from dicarboxylic acids and diamines, in particular the process for producing polyamide 66 from acid. adipic and hexamethylene diamine. This method of manufacturing polyamide 66 is known to those skilled in the art. The process for producing polyamide of the type of those obtained from dicarboxylic acids and diamines generally uses as raw material, a salt obtained by a mixture in stoichiometric quantity, generally in a solvent such as water, a diacid with a diamine. Thus, in the manufacture of poly (hexamethylene adipamide), adipic acid is mixed with hexamethylene diamine generally in water to obtain hexamethylene diammonium adipate better known as nylon salt or " Salt N ".

Thus, when the process of the invention uses a compound c) diacid, this compound c) and the compound b) diamine can be introduced, at least in part, in the form of a salt of compound c ) and compound b). In particular when the compound c) is adipic acid and the compound b) hexamethylenediamine, these compounds can be introduced at least partly in the form of N salt. This makes it possible to have a stoichiometric equilibrium.

The process of the invention generally leads to a random polymer.

The semi-aromatic polyamideimide obtained by the process of the invention comprises the recurring units indicated above. However, the polyamideimide obtained may also comprise the following bisimide repeating units:

And or

The presence of these recurring bisimide units in particular makes it possible to increase the crystallinity of the polyamideimide obtained.

The process of the invention is a simple process and easy to implement, which does not implement organic solvents that can be toxic.

The polyamideimide obtained according to the process of the invention can be used directly, without additional step for example to recover the polymer, as is the case for example in solution preparation processes.

The polyamideimide obtained at the end of the finishing step can be cooled and put into the form of granules.

The polyamideimide obtained by the process of the invention in molten form can be directly shaped or extruded and granulated, for subsequent shaping after melting.

The polyamideimide can be used for a large number of applications, in particular for the manufacture of yarns, fibers or filaments, films, or for shaping articles by injection molding, extrusion, extrusion blow molding. It can especially be used in technical plastic compositions.

The invention relates in a second object, a polyamideimide comprising the following recurring units:

AT

And or

R "is a hydrocarbon radical preferably comprising between 2 and 18 carbon atoms

Y is a trivalent aromatic hydrocarbon radical

Y 'is a tetravalent aromatic hydrocarbon radical

Or a polyamideimide comprising the following recurring units

And or

with R, R 'and R "are hydrocarbon radicals preferably comprising between 2 and 18 carbon atoms

R '"is an aromatic hydrocarbon radical, preferably comprising between 2 and 18 carbon atoms

Advantageously, such a polyamideimide does not comprise a unit derived from a diol monomer.

According to a particular embodiment of the invention, the polyamideimide advantageously comprises at least 60 mol%, preferably at least 80 mol% of recurring units A.

The polyamideimides of the invention have the advantage of being easily converted into the molten route, such as aliphatic polyamides, for example, which facilitates their shaping. In addition they present generally improved thermomechanical properties (in particular the HDT property "Heat Distortion Temperature"). Finally they show better water absorption properties compared to aliphatic polyamides, and a reduced thermal expansion compared with aliphatic polyamides.

The polyamideimide of the invention may be used alone or as part of a composition. It can particularly be used as an additive in thermoplastic polymer compositions comprising a thermoplastic matrix. He is involved in the composition as a reinforcing agent. The thermoplastic matrix is a thermoplastic polymer.

By way of example of polymers which may be suitable, mention may be made of: polylactones such as poly (pivalolactone), poly (caprolactone) and polymers of the same family; polyurethanes obtained by reaction between diisocyanates such as 1,5-naphthalene diisocyanate; p-phenylene diisocyanate, m-phenylene diisocyanate, 2,4-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 3, 3-dimethyl-4,4'-biphenyl diisocyanate, 4,4'-diphenylisopropylidene diisocyanate, 3,3'-dimethyl-4,4'-diphenyl diisocyanate, 3,3'-dimethyl-4,4 ' diphenylmethane diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, dianisidine diisocyanate, toluidine diisocyanate, hexamethylene diisocyanate, 4,4'-diisocyanatodiphenylmethane and compounds of the same family and long diols linear chains such as poly (tetramethylene adipate), poly (ethylene adipate), poly (1,4-butylene adipate), poly (ethylene succinate), poly (2,3-butylene succinate), polyether diols and composed of the same family; polycarbonates such as poly [methane bis (4-phenyl) carbonate], poly [1,1-bis (4-phenyl) carbonate), poly [diphenylmethane bis (4-phenyl) carbonate], poly [1 , 1 - cyclohexane bis (4-phenyl) carbonate] and polymers of the same family; polysulfones; polyethers; polyketones; polyamides such as poly (4-amino-butyric acid), poly (hexamethylene adipamide), poly (6-aminohexanoic acid), poly (m-xylylene adipamide), poly (p-xylylene sebacamide), poly ( 2,2,2-trimethyl hexamethylene terephthalamide), the poly (metaphenylene isophthalamide), poly (p-phenylene terephthalamide), and polymers of the same family; polyesters such as poly (ethylene azelate), poly (ethylene-1,5-naphthalate, poly (1,4-cyclohexane dimethylene terephthalate), poly (ethylene oxybenzoate), poly (para-hydroxy benzoate), poly (1,4-cyclohexylidene dimethylene terephthalate), poly (1,4-cyclohexylidene dimethylene terephthalate), polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate and polymers of the same family; poly (arylene oxides) such as poly (2,6-dimethyl-1,4-phenylene oxide), poly (2,6-diphenyl-1,4-phenylene oxide) and polymers of the same family, poly (arylene sulfites) such as poly (phenylene sulfide) and polymers of the same family, polyetherimides, vinyl polymers and their copolymers such as polyvinyl acetate, polyvinyl alcohol, polyvinyl chloride, polyvinyl butyral, polyvinylidene chloride, ethylene copolymers - vinyl acetate, and polymers of the same family, acrylic polymers, polyacrylates and their copolymers such as polyethyl acrylate, poly (n-butyl acrylate), polymethyl methacrylate, polyethyl methacrylate, poly (n-butyl methacrylate), poly (n-propyl methacrylate), polyacrylamide, polyacrylonitrile, poly (acrylic acid), ethylene-acrylic acid copolymers, ethylene-vinyl alcohol copolymers, copolymers of acrylonitrile, methyl methacrylate-styrene copolymers, ethylene-ethyl acrylate copolymers, methacrylate-butadiene-styrene copolymers, ABS, and polymers of the same family; polyolefins such as low density poly (ethylene), polypropylene, low density chlorinated poly (ethylene), poly (4-methyl-1-pentene), poly (ethylene), poly (styrene), and polymers of the same family; ionomers; poly (epichlorohydhnes); poly (urethane) such as diol polymerization products such as glycerine, trimethylolpropane, 1,2,6-hexanethol, 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'-dichlorodiphenyl sulfone; furan resins such as poly (furan); cellulose-ester plastics such as cellulose acetate, cellulose acetate butyrate, 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.

According to a particular variant of the invention, the thermoplastic matrix is a polymer comprising star or H macromolecular chains, and optionally linear macromolecular chains. The polymers comprising such star or H macromolecular chains are for example described in the documents FR 2 743 077, FR 2 779 730, US 5 959 069, EP 0 632 703, EP 0 682 057 and EP 0 832 149.

According to another particular variant of the invention, the thermoplastic matrix of the invention is a random tree type polymer, preferably a copolyamide having a random tree structure. These copolyamides of random tree structure and their method of production are described in particular in WO 99/03909.

The thermoplastic matrix of the invention may also be a composition comprising a linear thermoplastic polymer and a thermoplastic star, H and / or tree polymer as described above.

The compositions of the invention may also comprise a hyperbranched copolyamide of the type of those described in WO 00/68298.

The compositions of the invention may also comprise any combination of thermoplastic star polymer, H, tree, hyperbranched copolyamide described above.

As another type of polymer matrix that can be used in the context of the invention, there may be mentioned thermostable polymers: these polymers are preferably infusible or have a softening point greater than 180 ^° C., preferably> 200 ⁰ C, or higher. These thermostable polymers may for example be chosen from aromatic polyamides, polyamide imides such as polytrimellamide imides, or polyimides such as the polyimides obtained according to document EP 0119185, known commercially under the trademark P84. The aromatic polyamides may be as described in patent EP 0360707. They may be obtained according to the process described in patent EP 0360707.

As another polymeric matrix, there may also be mentioned viscose, cellulose, cellulose acetate and so on.

The polymer matrix of the invention may also be of the type of polymers used in adhesives, such as copolymers of plastisol vinyl acetates, acrylic latices, urethane latices, PVC plastisol, etc.

Among these polymer matrices, semicrystalline polyamides, such as polyamide 6, polyamide 6.6, polyamide 11, polyamide 12, polyamide 4, polyamides 4-6, 6-10, are particularly preferred. 6-12, 6-36, 12-12, semi-aromatic polyamides obtained from terephthalic and / or isophthalic acid such as the polyamide marketed under the trade name AMODEL; polyesters such as PET, PBT, PTT; polyolefins such as polypropylene, polyethylene; aromatic polyamides, polyamide imides or polyimides; latex such as acrylic latex and urethane; PVC, viscose, cellulose, cellulose acetate; their copolymers and alloys.

The compositions may contain any other additives that may be used, for example reinforcing fillers, flame retardants, UV stabilizers, heat, mattifying agents such as titanium dioxide.

The compositions according to the invention are preferably obtained by melt blending of the thermoplastic polymer and the polyamideimide. The mixture can for example be made using an extrusion device, for example a single screw or double screw mixer. The weight ratio of polyamideimide in the composition is advantageously between 1 and 99%, preferably between 5 and 30%.

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

The compositions according to the invention can also be put into the form of son, fibers, filaments by melt-spinning.

Other details or advantages of the invention will appear more clearly in view of the examples given below.

EXAMPLES

characterizations

Absolute molar mass: determined by gel permeation chromatography (GPC) in dichloromethane (+ trifluoroacetic anhydride), then by triple detection by refractometry R1, UV absorption and viscosimethe.

Imide cyclization rate: determined by ¹ H NMR at 300 K in deuterated formic acid, using a 300 MHz Bruker DRX apparatus

Melting temperature (T _f ) and associated enthalpy (ΔHf), glass transition temperature (T ₉ ), cooling crystallization temperature (T _c ): determined by differential scanning calorimetry (DSC) using a Perkin Elmer Pyris 1 device, at a rate of 10 ° C / min.

Acid and amino terminal group contents: assayed by potentiometry

Viscosity index (IV): measured according to ISO EN 307 Example 1 Preparation of a Polyamide Imide PAI 66 / 6TMA 90/10

132.37 g (0.505 mol) of N salt (1: 1 salt of hexamethylene diamine and of adipic acid), 11.78 g of trimellitic acid (TMLA) (0.056 mol) are introduced into a polymerization reactor, 19.99 g of a solution of hexamethylenediamine (HMD) in solution in water at 32.6% by weight (0.056 mol) and 123.65 g of demineralized water and 2 g of antifoaming agent.

The polyamideimide is manufactured according to a standard polyamide 66 polymerization process.

The polymer obtained is cast in the form of rod, cooled and granulated by cutting rushes.

The polymer obtained has the following characteristics:

Mn = 9 700 g / mol

Tg = 63 ^° C., Tc = 204.2 ^° C., mp = 247.2 ° C.

The ¹ H NMR analysis indicated complete cyclization to the imide.

Examples 2 to 7

In Examples 2 to 7 are prepared, according to a standard method of polymerization of polyamide 66 type, as in Example 1, polyamideimides of PAI 66 / 6TMA type of molar composition 80/20 (Example 2), 67/33 ( Example 3), 60/40 (Example 4), 50/50 (Example 5), 30/70 (Example 6),

15/85 (Example 7).

The compositions (all compositions comprise 2 g of antifoaming agent) and characterizations of these polymers are mentioned in Table 1 below. Table 1

¹ H NMR analysis indicates total imide cyclization for Examples 2 to 7. Example 8: Preparation of a polyamideimide from trimellitic anhydride

In this example trimellitic anhydride is used in place of trimellitic acid.

115.37 g of N salt, 21.80 g of 97% trimellitic anhydride, 39.19 g of hexamethylenediamine solution at 32.6% by weight in water and 9.9 g of solution are introduced into the polymerization reactor. , 39 g of demineralized water and 2 g of antifoaming agent.

The polyamideimide is manufactured according to a standard polyamide 66 polymerization process, as in Example 1.

The polymer obtained has the following characteristics:

Mn = 9,800 g / mol

Tc = 186.6 ^° C., mp = 234.5 ^° C.

The ¹ H NMR analysis indicated complete cyclization to the imide.

The analyzes do not show any major differences between the polymers synthesized with trimellitic anhydride or with trimellitic acid.

Example 9 Preparation of a Polyamideimide PAI 6TMA

In a polymerization reactor are introduced 99.90 g of trimellitic acid, 169.49 g of HMD in water at 32.6% by weight and 27.08 g of demineralized water and 2 g of antifoaming agent.

The polyamideimide is manufactured according to a standard polyamide 66 polymerization process, as in Example 1. The polymer obtained is cast in the form of rod, cooled and granulated by cutting rushes.

The polymer obtained has the following characteristics:

Mn = 9,800 g / mol

Tg = 120.2 ^° C.

The polymer is amorphous.

The ¹ H NMR analysis indicated complete cyclization to the imide.

Example 10 Preparation of a Polyamideimide PAI 66 / 6PMDA 95/5

140.43 g of N salt, 7.16 g of pyromellitic acid, 10.04 g of HMD in water at 32.6% by weight and 130.58 g of water are introduced into a polymerization reactor. demineralized and 2g of antifoaming agent.

The polymer obtained has the following characteristics:

Mn = 9,400 g / mol

Tc = 220.2 ^° C., Tm = 255.1 ^° C.

The ¹ H NMR analysis indicated complete cyclization to the imide.

Example 11 Preparation of a Polyamideimide PAI 66 / 6T / 6TMA 57/38/5

82.11 g of N salt (1: 1 salt of hexamethylene diamine and adipic acid), 58.92 g of a 6T salt (1: 1 salt) are introduced into a polymerization reactor. hexamethylene diamine and terephthalic acid), 5.84 g of trimellitic acid

(TMLA), 10.48 g of a solution of hexamethylenediamine (HMD) in solution in water at 32.65% by weight and 137.3 g of demineralised water and 2 g of antifoaming agent.

The polymer obtained has the following characteristics:

Tc = 238.4 ⁰ C, mp = 271, 9 ° C

The ¹ H NMR analysis indicated complete cyclization to the imide.

Examples 12 to 17: Preparation of compositions comprising a polyamide and a polyamideimide according to the invention.

Compositions comprising a polyamide PA 66 and a polyamideimide PAI 6TMA were prepared in a micro-extruder ("micro-compounder")

DSM MIDI 2000 (15 cm ³ ) at a temperature of 275 ^° C. The proportions by weight of PA 66 / PAI 6TMA compositions prepared are as follows: 90/10, 75/25,

50/50, 25/75, 10/90.

The polyamide used is a PA 66 has the following characteristics: IV = 138.7 ml.g ^"1, GTA = 44.9 ^{meq.kg" 1,} GTC = 76.9 meq.kg ^"1. The polyamideimide used is polyamidimide of Example 9.

The polyamide PA66 and the polyamideimide PAI 6TMA are mixed in the micro-extruder at a temperature of 275 ^° C., and injected into a mold at 70 ^° C. (injection module) in the form of bars of dimensions 62 × ¹² × 4 mm ³ .

These bars are conducted thermal analyzes in DSC to determine the melting temperature and the degree of crystallinity. It is observed that PA 66 reaches the same degree of crystallinity regardless of the composition of the mixture: PAI 6TMA does not interfere with the crystallization of PA 66. Dynamic mechanical analyzes (DMA) are performed on specimens cut in these bars. A sinusoidal stress is applied in 3-point bending with double embedding (frequency 1 hz and amplitude 0.05%) and the analysis by DMA is carried out between +20 and +260 ⁰ C (rise at + 2.5 ° C / min). These measurements are made on a Rheometrics brand RSA2 dynamic measuring machine (DMA).

On these bars are carried out dynamic mechanical analyzes to determine the miscibility by the research of transition temperatures α (Ta) (equivalent of Tg in dynamic mechanical analysis) and the level of the elastic modulus (E ') at 90 ^° C. We observe two transition temperatures α, sign of immiscibility between the two polymers. The elastic modulus at 90 ^° C. of PA 66 is increased in the presence of PAI 6TMA.

Table 2

N.M. = No Measurable: existence of a Ta but it can not be measured.

Claims

Process for the preparation of semi-aromatic polyamideimide by melt polymerization of at least the following monomers:

b) at least one diamine compound, preferably aliphatic diamine,

c) Optionally at least one diacid compound

When all the carboxyl groups of the compound a) form an intramolecular anhydride function or can form an intramolecular anhydride function, the molar proportion of compound c) relative to the sum of the compounds a) and c) is greater than or equal to 0.5% , advantageously greater than or equal to 25%, preferably greater than or equal to 50%

2. Method according to claim 1, characterized in that at least 45 mol%, preferably at least 50 mol% of the diamine compound is an aliphatic, cycloaliphatic or arylaliphatic diamine

3. Method according to claim 1 or 2, characterized in that the compound a) comprises three or four carboxyl groups

4. Method according to claim 3, characterized in that the compound a) comprises three or four carboxylic acid functions

5. Method according to one of the preceding claims, characterized in that the compound a) has the following formula (I):

Z- (COOH) ₃

in which Z is a trivalent aromatic hydrocarbon radical

6. Process according to claim 5, characterized in that Z contains between 6 and 18 carbon atoms.

7. Process according to one of the preceding claims, characterized in that the compound a) is chosen from trimellitic acid, pyromellitic acid, or their anhydrides, their esters or their amides.

8. Method according to one of the preceding claims, characterized in that the compound b) has the following formula (II):

H ₂ NR-NH ₂ (II)

in which R is a divalent aliphatic, cycloaliphatic, arylaliphatic or aromatic hydrocarbon radical

9. Process according to claim 8, characterized in that the radical R has between 2 and 18 carbon atoms.

10. Method according to one of the preceding claims, characterized in that the compound b) is an aliphatic diamine

11. Method according to one of the preceding claims, characterized in that the compound c) has the following formula (III):

HOOC-R'-COOH (III)

in which R 'is a divalent aliphatic, cycloaliphatic, arylaliphatic or aromatic hydrocarbon radical

12. The method of claim 11, characterized in that the radical R 'has between 2 and 18 carbon atoms.

13. Method according to one of the preceding claims, characterized in that the compound c) is an aliphatic diacid

14. Method according to one of the preceding claims, characterized in that it does not comprise lactam monomer or amino acid aliphatic, preferably no lactams or amino acids

15. Process according to one of the preceding claims, characterized in that it does not comprise any diol monomer.

16. Polyamideimide comprising the following recurring units

And or

R "is a hydrocarbon radical preferably comprising between 2 and 18 carbon atoms

Y is a trivalent aromatic hydrocarbon radical

Y 'is a tetravalent aromatic hydrocarbon radical

17. Polyamideimide according to claim 16, characterized in that it comprises at least 60 mol%, preferably at least 80 mol% of repeating units A

18. Polyamideimide according to claim 16 or 17, characterized in that it does not comprise a unit derived from a diol monomer.

19. Polyamideimide comprising the following recurring units:

And or

R '"is an aromatic hydrocarbon radical, preferably comprising between 2 and 18 carbon atoms Y is a trivalent hydrocarbon radical, aromatic or aliphatic, preferably aromatic

20. A thermoplastic polymer composition comprising:

a) the semi-aromatic polyamideimide according to one of claims 16 to 19 or obtained by the process according to one of claims 1 to 15;

b) -a thermoplastic matrix

21. Article obtained by shaping from the composition according to claim 20, preferably by molding, injection molding, injection / blowing extrusion / blowing, extrusion or spinning,